Process for separating molecular species

ABSTRACT

Crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , SiO 2  and PO 2  framework oxide units are disclosed. The molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: 
     
         mR: (EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 
    
     wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;m&#34; represents the molar amount of &#34;R&#34; present per mole of (EL w  Al x  P y  Si z )O 2  ; &#34;EL&#34; represents at least one element capable of forming a framework oxide unit; and &#34;w&#34;, &#34;x&#34;, &#34;y&#34; and &#34;z&#34; represent the mole fractions of elements(s) &#34;EL&#34;, aluminum, phosphorus and silicon, respectively, present as framework oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

This is a divisional of copending application(s) Ser. No. 07/182,738 filed on 4/18/88 which is a division of Ser. No. 06/600,312 filed 4/13/84, now U.S. Pat. No. 4,793,984.

FIELD OF THE INVENTION

The instant invention relates to a novel class of three-dimensional microporous crystalline molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to novel molecular sieves having at least one element capable of forming a framework oxide units, e.g., "ELO₂ ", with tetrahedral oxide units of aluminum (AlO₂ ⁻), phosphorus (PO₂ ⁺) and silicon (SiO₂). These compositions may be prepared hydrothermally from gels containing reactive compounds of silicon, aluminum and phosphorus and at least one additional element capable of forming a framework oxide unit, and preferably at least one organic templating agent which may function in part to determine the course of the crystallization mechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO₂ and SiO₂ tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO₂ tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 Å or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO₂ and PO₂ tetrahedra and have electrovalently neutral framework as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

In copending and commonly assigned application Ser. No. 400,438, filed July 26, 1982 (now U.S. Pat. No. 4,440,871), there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensions crystal framework of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral unites and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.

In copending and commonly assigned application Ser. No. 480,738, filed Mar. 31, 1983 (now U.S. Pat. No. 4,500,651) there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,334, filed July 15, 1983 (now U.S. Pat. No. 4,567,029), there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,335, filed July 15, 1983 (now U.S. Pat. No. 4,683,217), there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO₂, AlO₂ and PO₂ tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain species and by the existence of species heretofore unknown for binary and ternary molecular sieves.

The instant invention relates to new molecular sieve compositions having at least one element other than silicon, aluminum and phosphorus where such element is capable of forming a framework oxide unit with AlO₂ ⁻, PO₂ ⁺, and SiO₂ tetrahedral oxide units.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class of molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO₂, AlO₂ ⁻, PO₂ ⁺ and ELO₂ ^(n) units wherein "EL" represents at least one element present as a framework oxide unit "ELO₂ ^(n) " with charge "n" where "n" may be -3, -2, -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.

The member of this novel class of compositions have crystal framework structures of SiO₂, AlO₂ ⁻, PO₂ ⁺ and ELO₂ ^(n) framework oxide units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value from zero to about 0.3; "EL" represents at least one element capable of forming a framework oxide unit as hereinafter described; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. "EL" denominates the elements present in addition to aluminum, phosphorus and silicon and may be a single element or may be two or more elements such that the molecular sieves contain one or more framework oxide units "ELO₂ ^(n) " in addition to framework tetrahedral oxide units SiO₂, AlO₂ ⁻ and PO₂ ⁺.

The molecular sieves of the instant invention will be generally referred to by the acronym "ELAPSO" to designate element(s) "EL" in an oxide framework of SiO₂, AlO₂ ⁻, PO₂ ⁺ and ELO₂ ^(n) oxide units. Actual class members will be identified by replacing the "EL" of the acryonym with the element(s) present as a ELO₂ ^(n) oxide unit(s). For example "CoAPSO" designates a molecular sieve comprised of SiO₂, AlO₂ ⁻, PO₂ ⁺ and CoO₂ ⁻² (and/or CoO₂ ⁻¹) framework oxide units, and "CoZnAPSO" designates a molecular sieve having SiO₂, AlO₂ ⁻, PO₂ ⁺, CoO₂ ⁻² (and/or CoO₂ ⁻¹) and ZnO₂ ⁻² framework oxide units. To identify various structural species which make up each of the subgeneric classes, each species is assigned a number and is identified as "ELAPSO-i" wherein "i" is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be characterized by a numbering system.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class of three-dimensional microporous crystalline molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO₂, AlO₂ ⁻, PO₂ ⁺ and ELO₂ ^(n) framework oxide units wherein "EL" represents at least one element capable of forming a framework oxide unit "ELO₂ ^(n) " with charge "n" where "n" is -3, -2, -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and accordingly find wide use as adsorbents and catalysts.

The ELAPSO compositions are formed with elements capable of forming framework oxide units in the presence of SiO₂, AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxide units where element "EL" is at least one element capable of forming a three dimensional oxide framework in the presence of aluminum, phosphorus and silicon oxide units, and has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 Angstroms, has a cation electronegativity between about 125 kcal/g-atom and about 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D°, is greater than about 59 kcal/mole at 298° K. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to designate the element (EL) bonded to oxygen. For the purposes of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The "T-O" distance denominates the bond length of the "T-O" bond where "T" is element(s) "EL" occupying the tetrahedral cation site and is related to the Shannon/Prewitt crystal or ionic radii. Elements known to occur in tetrahedral coordination with oxygen are discussed in: Joseph V. Smith, "Feldspar Minerals", Springer-Verlag, Berlin, New York, Vol. I, pp. 55-65 and 106-113 (1974); R. D. Shannon, Acta. Cryst., A32, p. 751 (1976); R. D. Shannon, C. T. Prewitt, Acta. Cryst., B25, p. 925 (1969); and F. Donald Bloss, "Crystallography and Crystal Chemistry", Holt, Rinehart and Winston, Inc., New York, pp. 278-279 (1971). The "T-O" distance is calculated according to the procedures heretofore employed and as discussed in, R. D. Shannon, Acta Cryst., A32, p. 751 (1976) and R. D. Shannon, C. T. Prewitt, Acta Cryst., B25, p. 925 (1969), based, repspectively, on the ionic and crystal radius of oxide ion, O²⁻, of 1.40 Angstroms and 1.26 Angstroms. The cation electronegtivity of element(s) "EL" is determined consistent with the procedure set forth in A. S. Povarennykh, "Crystal Chemical Classification of Minerals", Vol. I, translation from Russian by J. E. S. Bradley, Plenum Press, New York-London, p. 32 (1972). The bond dissociation energy of "M-O" is determined according to the procedures discussed in: V. I. Vedeneyev, L. V. Gurvich, V. N. Kondrat'Yev, V. A. Medvedev and Ye. L. Frankevich, "Bond Energies, Ionization Potentials and Electron Affinities," New York, St. Martins Press, English Translation, p. 29ff (1966); "The Oxide Handbook", 2nd Ed., G. V. Samsonov, ED., translation from Russian by R. K. Johnston, IFI/Plenum Data Company, pp. 86-90 (1982); and "Bond Dissociation Energies in Simple Molecules", B deB. Darwent, NSRSS-NBS 31, U.S. Dept. of Commerce, National Bureau of Standards, pp. 9-47 (1970).

Further embodiments of the instant invention relate to the molecular sieves as above defined being characterized by element(s) "EL" characterized by at least one of the following criteria:

(1) "EL" is characterized by an electronic orbital configuration selected from the group consisting of d⁰, d¹, d², d⁵, d⁶, d⁷, or d¹⁰ where the small crystal field stabilization energy of the metal ligand "-OM" favors tetrahedral coordination of element EL ("EL" denominated here also as "M") with O²⁻, as discussed in "Inorganic Chemistry" J. E. Huheey, Harper Row, p. 348 (1978):

(2) "EL" is characterized as capable of forming stable oxo or hydroxo species in aqueous solution as evidenced by a first hydrolysis constant, K₁₁, greater than 10⁻¹⁴, as discussed in "The Hydrolysis of Cations", C. F. Baes and R. E. Mesmer, John Wiley & Sons (1976);

(3) "EL" is selected from the group of elements known to occur in crystal structure types geometrically related to the different silica modifications, quartz, cristobalite or tridymite, as discussed in E. Parthe, "Crystal Chemistry of Tetrahedral Structures", Gordon and Breach, New York, London, pp. 66-68 (1964); and

(4) "EL" is an element which in its cation form is classified by Pearson, (J. E. Huheey, "Inorganic Chemistry", Harper & Row, p. 276 (1978)) as "hard" or "borderline" acids which interact with the "hard" base O²⁻ to form more stable bonds than the cations classified as "soft" acids.

In one embodiment of the invention element "EL" is preferably at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.

The relative amounts of silicon, aluminum, phosphorus and element(s) "EL" are expressed by the empirical chemical formula (anhydrous):

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "w", "x", "y" and "z" represent the mole fractions of said element(s) "EL", aluminum, phosphorus, and silicon, respectively. When "EL" comprises two or more elements, "w" represents the mole fractions of said elements (EL₁, EL₂, EL₃, EL₄, etc.) and "w" equals the sum of "w₁ ", "w₂ ", "w₃ ", "w₄ ", etc., wherein "w₁ ", "w₂ ", "w₃ ", "w₄ " and etc. represent the individual mole fractions of elements EL₁, EL₂, EL₃, EL₄ and etc. and each has a value of at least 0.01.

The molecular sieves of the instant invention have three-dimensional microporous crystalline framework structures of ELO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ framework oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 Angstroms, has a cation electronegativity between about 125 kcal/g-atom to 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D°, is greater than about 59 kcal/mole at 298° K; and "w", "x", "y" and "z" represent the mole fractions of element(s) "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to dominate the element (EL) bonded to oxygen. For the purpose of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of FIG. 1, said points A, B, C, D and E of FIG. 1 having the following values for "w", "x", "y", and "z":

    ______________________________________                                                Mole Fraction                                                           Point    x           y           (z + w)                                       ______________________________________                                         A        0.60        0.39-(0.01)p                                                                               0.01(p + 1)                                   B        0.39-(0.01p)                                                                               0.60        0.01(p + 1)                                   C        0.01        0.60        0.39                                          D        0.01        0.01        0.98                                          E        0.60        0.01        0.39                                          ______________________________________                                    

where "p" is an integer corresponding to the number of elements "EL" in the (EL_(w) Al_(x) P_(y) Si_(z))O₂ constituent and is preferably an integer from one (1) to fourteen (14).

In a preferred subclass of the ELAPSO molecular sieves the values of "w", "x", "y" and "z", where "w" is as above defined, in the above formula are within the tetragonal compositional area defined by points a, b, c and d of the ternary diagram which is FIG. 2, said points a, b, c and d representing the following values for "w", "x", "y" and "z";

    ______________________________________                                                Mole Fraction                                                           Point    x           y           (z + w)                                       ______________________________________                                         a        0.60        0.39-0.01p  0.01(p + 1)                                   b        0.39-(0.01p)                                                                               0.60        0.01(p + 1)                                   c        0.10        0.55        0.35                                          d        0.55        0.10        0.35                                          ______________________________________                                    

where "p" is as above defined.

While it is believed that the elements "EL", aluminum, phosphorus and silicon in the framework constituents are present in tetrahedral coordination with oxygen, i.e. as tetrahedral oxide units, it is theoretically possible that some fraction of these framework constituents are present in coordination with five or six oxygen atoms. The convenient reference herein to the framework oxide units are represented by formulae which indicate tetrahedral oxide units, although as above noted other than tetrahedral coordination may exist. It is not, moreover, necessarily the case that all the elements "EL" of any given synthesized product be part of the framework in the aforementioned types of coordination with oxygen. Some of each constituent may be in some as yet undetermined form.

The ELAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

ELAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing active sources of element(s) "EL", silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent which is preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at an effective temperature which is preferably between about 50° C. and about 250° C., more preferably between 100° C. and 200° C., until crystals of the ELAPSO product are obtained, usually an effective crystallization time of from several hours to several weeks. Generally, effective crystallization times of from about 2 hours to about 30 days are employed with typically from 4 hours to about 20 days being employed to obtain ELAPSO products. The product is recovered by any convenient method such as centrifugation or filtration.

In synthesizing the ELAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of molar ratios as follows:

    aR:(EL.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; "EL" represents at least one element, as herein before described, capable of forming a framework oxide unit, ELO₂ ^(n), with SiO₂, AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxide units; "n" has a value of -3, -2, -1, 0 or +1; and "r", "s", "t", "u" represent the mole fractions of element "EL", aluminum, phosphorus, and silicon respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions " r", "s", "t", and "u" are generally defined as being within the pentagonal compositional area defined by points E, F, G, H, and I of the ternary diagram of FIG. 3. Points E, F, G, H, and I of FIG. 3 have the following values for "r", "s", "t", and "u":

    ______________________________________                                         Mole Fraction                                                                  Point   s             t      (u + r)                                           ______________________________________                                         F       0.60          0.38   0.02                                              G       0.38          0.60   0.02                                              H       0 01          0.60   0.39                                              I       0.01          0.01   0.98                                              J       0.60          0.01   0.39                                              ______________________________________                                    

In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "r", "s", "t", and "u" such that (r+s+t+u)=1.00 mole, whereas in the examples the reaction mixtures may be expressed in terms of molar oxide ratios normalized to the moles of P₂ O₅. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of each component (including the template and water) by the total number of moles of elements "EL", aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.

In forming reaction mixtures from which the ELAPSO molecular sieves are formed an organic templating agent is preferably employed and may be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorous and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quarternary phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formula R₄ X⁺ wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂ N₂)(OH₂ ]_(x) wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents may either produce mixtures of the desired ELAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include: tetramethylammonium; tetraethylammonium; tetrapropylammonium; tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo(2,2,2)octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of ELAPSO, i.e., a single templating agent may, with proper manipulation of the reaction conditions, direct the formation of several ELAPSO compositions, and a given ELAPSO composition can be produced using several different templating agents.

The source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silica containing clays silicic acid or alkali metal silicate and mixtures thereof.

The most suitable phosphorus source yet found for the present process is phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory, and so also have crystalline or amorphous aluminophosphates such as the AlPO₄ compositions of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide do not, apparently, serve as reactive sources of phosphorus, but these compounds do function as templating agents. Conventional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.

The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, aluminum-containing clays, sodium aluminate and aluminum trichloride, can be employed but are not preferred.

The element(s) "EL" can be introduced into the reaction system in any form which permits the formation in situ a of reactive form of the element, i.e., reactive to form a framework oxide unit of element "EL". Compounds of element(s) "EL" which may be employed include oxides, hydroxides, alkoxides, nitrates, sulfates, halides, carboxylates and mixtures thereof. Representative compounds which may be employed include: carboxylates of arsenic and beryllium; cobalt chloride hexahydrate, alpha cobaltous iodide; cobaltous sulfate; cobalt acetate; cobaltous bromide; cobaltous chloride; boron alkoxides; chromium acetate; gallium alkoxides; zinc acetate; zinc bromide; zinc formate; zinc iodide; zinc sulfate heptahydrate; germanium dioxide; iron (II) acetate; lithium acetate; magnesium acetate; magnesium bromide; magnesium chloride; magnesium iodide; magnesium nitrate; magnesium sulfate; manganese acetate; manganese bromide; manganese sulfate; titanium tetrachloride; titanium carboxylates; titanium acetate; zinc acetate; and the like.

While not essential to the synthesis of ELAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ELAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.

After crystallization the ELAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized ELAPSO generally contains within its internal pore system at least one form of any templating agent employed in its formation. Most commonly this organic moiety, derived from any organic template, is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety may be an occluded molecular species in a particular ELAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the ELAPSO product and must be removed by calcining the ELAPSO at temperatures of 200° C. to 700° C. to thermally degrade the organic species. In some instances the pores of the ELAPSO compositions are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof may be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of ELAPSO species wherein any organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:

    mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of element(s) "EL", aluminum, phosphorous and/or silicon, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the syntheses process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized ELAPSO material.

Since the present ELAPO compositions are formed from AlO₂ ⁻, PO₂ ⁺, SiO₂ and ELO₂ ^(n) framework oxide units which, respectively, have a net charge of -1, +1, 0 and "n", where "n" is -3, -2, -1, 0 or +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO₂ ⁻ tetrahedra and charge-balancing cations. In the instant compositions, an AlO₂ ⁻ tetrahedron can be balanced electrically either by association with a PO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, a cation of the element "EL" present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, an ELO₂ ^(n) oxide unit can be balanced electrically by association with PO₂ ⁺ tetrahedra, a simple cation such as an alkali metal cation, a cation of the metal "EL", organic cations derived from the templating agent, or other divalent or polyvalent metal cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH⁻ respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].

The ELAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3 Å in diameter. Ion exchange of ELAPSO compositions will ordinarily be possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized ELAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The ELAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.

In the examples a stainless steel reaction vessel is utilized which is lined with an inert plastic material, polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each ELAPSO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the admixed reagents retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, unless otherwise specified, each intermediate mixture as well as the final reaction mixture was stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2° (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2θ where θ is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "I_(o) " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.

Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, New Jersey, with appropriate computer interface.

As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about ±0.4° (denotes plus or minus 0.4) on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak, and very weak, respectively.

In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.

The molecular sieves of the instant invention may be characterized by their x-ray powder diffraction patterns and such may have one of the x-ray patterns set forth in the following Tables A through W, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:

                  TABLE A                                                          ______________________________________                                         (ELAPSO-5)                                                                     2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.2-7.7      12.28-11.48                                                                               m-vs                                                   19.4-19.9    4.58-4.46 w-m                                                     20.85-21.3   4.26-4.17  w-vs                                                   22.1-22.6    4.02-3.93  m-vs                                                   25.6-26.1    3.480-3.414                                                                              vw-m                                                    ______________________________________                                    

                  TABLE B                                                          ______________________________________                                         (ELAPSO-11)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.8-8.2      11.19-10.85                                                                              m-s                                                     9.0-9.8      9.83-9.03 vw-vs                                                   12.8-13.6    6.92-6.51 vw-m                                                    19.9-20.5    4.46-4.33 m-s                                                     20.8-21.8    4.27-4.08  m-vs                                                   22.0-22.6    4.04-3.93  m-vs                                                   22.6-23.1    3.93-3.85 vw-vs                                                   23.1-23.5    3.85-3.79  w-vs                                                   ______________________________________                                    

                  TABLE C                                                          ______________________________________                                         (ELAPSO-14)                                                                    2θ     d(Å) Relative Intensity                                       ______________________________________                                         8.6-8.9      10.3-9.93                                                                               vs                                                       13.0         6.81     w                                                        21.9-22.2    4.06-4.00                                                                               w                                                        25.4         3.51     w                                                        27.5         3.24     w                                                        29.7         3.01     w                                                        ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         (ELAPSO-16)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         11.3-11.6    7.83-7.63  w-vs                                                   18.55-18.9   4.78-4.70 vm-m                                                    21.85-22.2   4.07-4.00  m-vs                                                   22.8-23.3    3.900-3.818                                                                              w-m                                                     26.4-27.3    3.370-3.267                                                                              w-m                                                     29.6-29.9    3.018-2.988                                                                              w-m                                                     ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         (ELAPSO-17)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.70-7.75    11.5-11.4 vs                                                      13.4         6.61       s-vs                                                    15.5-15.55  5.72-5.70 s                                                       19.65-19.7   4.52-4.51 w-s                                                     20.5-20.6    4.33-4.31 vs                                                       31.8-32.00  2.812-2.797                                                                              w-s                                                     ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         (ELAPSO-18)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                          9.6-9.65    9.21-9.16 vs                                                       15.5-15.55  5.72-5.70 m                                                       16.9-17.1    5.25-5.19 m                                                       20.15-20.25  4.41-4.39 m                                                       20.95-21.05  4.24-4.22 m                                                       31.8-32.5    2.814-2.755                                                                              m                                                       ______________________________________                                    

                  TABLE G                                                          ______________________________________                                         (ELAPSO-20)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.8-14.2    6.42-6.23  m-vs                                                    19.6-20.15  6.53-4.41 m                                                       24.1-24.7    3.695-3.603                                                                               m-vs                                                   27.9-28.6    3.198-3.121                                                                              w                                                        31.3-32.05  2.861-2.791                                                                              w                                                       34.35-35.0   2.610-2.601                                                                              w-m                                                     ______________________________________                                    

                  TABLE H                                                          ______________________________________                                         (ELAPSO-31)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         8.4-9.5      10.53-9.31                                                                               w-s                                                     20.2-20.4    4.40-4.35 m                                                       22.0-22.1    4.040-4.022                                                                              m                                                       22.5-22.7    3.952-3.92                                                                               vs                                                      31.6-31.8    2.831-2.814                                                                              w-m                                                     ______________________________________                                    

                  TABLE J*                                                         ______________________________________                                         (ELAPSO-33)                                                                    2θ      d(Å) Relative Intensity                                      ______________________________________                                         9.25-9.55     9.56-9.26                                                                               w-m                                                     12.5-12.9     7.08-6.86                                                                               vs                                                      16.9-17.3     5.25-5.13                                                                               w-m                                                     20.45-20.9    4.34-4.25                                                                               w-m                                                     23.85-24.25   3.73-3.67                                                                               w-m                                                     26.05-26.35   3.42-3.38                                                                               w-m                                                     27.3-27.6     3.27-3.23                                                                               vs                                                      ______________________________________                                          *as-synthesized form                                                     

                  TABLE K*                                                         ______________________________________                                         (ELAPSO-33)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         13.15-13.4   6.73-6.61 vs                                                      18.05-18.35  4.91-4.83 m                                                       18.4-18.6    4.82-4.77 m                                                       26.55-26.7   3.36-3.34 m                                                       32.0-32.1    2.80-2.79 m                                                       ______________________________________                                          *calcined form                                                           

                  TABLE L                                                          ______________________________________                                         (ELAPSO-34)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         9.3-9.8      9.51-9.03  m-vs                                                   12.6-13.2    7.03-6.71 w-m                                                     15.8-16.3    5.61-5.44 vw-m                                                    20.25-21.2   4.39-4.19  w-vs                                                   24.8-25.4     3.59-3.507                                                                              vw-m                                                    30.0-30.9    2.979-2.894                                                                              vw-m                                                    ______________________________________                                    

                  TABLE M                                                          ______________________________________                                         (ELAPSO-35)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 vw-vs                                                   13.1-13.7    6.76-6.46 vw-vs                                                   17.0-17.6    5.22-5.04 w-s                                                      20.6-21.25  4.31-4.18 vw-m                                                    21.6-22.3    4.11-3.99  m-vs                                                   28.1-28.8    3.175-3.100                                                                              vw-m                                                    ______________________________________                                    

                  TABLE N                                                          ______________________________________                                         (ELAPSO-36)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.45-8.0     11.14-11.05                                                                              vs                                                      8.1-8.3      10.91-10.65                                                                              w-m                                                     16.3-16.6    5.44-5.34 w-m                                                     18.9-19.4    4.70-4.57 w-m                                                     20.7-21.0    4.29-4.23 w-m                                                     ______________________________________                                    

                  TABLE O                                                          ______________________________________                                         (ELAPSO-37)                                                                    2θ     d(Å)  Relative Intensity                                      ______________________________________                                         6.1-6.3      14.49-14.03                                                                              vs                                                      15.5-15.7    5.72-5.64 w-m                                                     18.5-18.8    4.80-4.72 w-m                                                     23.5-23.7    3.79-3.75 w-m                                                     26.9-27.1    3.31-3.29 w-m                                                     ______________________________________                                    

                  TABLE P                                                          ______________________________________                                         (ELAPSO-39)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.2-9.6     9.61-9.21 m                                                        13.1-13.5   6.76-6.56 m                                                        17.8-18.4   4.98-4.82 w-m                                                      20.8-21.3   4.27-4.17 m-vs                                                      22.2-22.85  4.00-3.892                                                                              m-vs                                                      26.4-27.05 3.376-3.296                                                                              w-m                                                      ______________________________________                                    

                  TABLE Q                                                          ______________________________________                                         (ELAPSO-40)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.5-7.7     11.79-11.48                                                                              vw-m                                                     8.0-8.1     11.05-10.94                                                                              s-vs                                                     12.4-12.5   7.14-7.08 w-vs                                                     13.6-13.8   6.51-6.42 m-s                                                      14.0-14.1   6.33-6.28 w-m                                                      27.8-28.0   3.209-3.187                                                                              w-m                                                      ______________________________________                                    

                  TABLE R                                                          ______________________________________                                         (ELAPSO-41)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         13.6-13.8   6.51-6.42 w-m                                                      20.5-20.6   4.33-4.31 w-m                                                      21.1-21.3   4.21-4.17 vs                                                       22.1-22.3   4.02-3.99 m-s                                                      22.8-23.0   3.90-3.86 m                                                        23.1-23.4   3.82-3.80 w-m                                                      25.5-25.9   3.493-3.44                                                                               w-m                                                      ______________________________________                                    

                  TABLE S                                                          ______________________________________                                         (ELAPSO-42)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.15-7.4    12.36-11.95                                                                              m-vs                                                     12.5-12.7   7.08-6.97 m-s                                                      21.75-21.9   4.09-4.060                                                                              m-s                                                       24.1-24.25 3.69-3.67 vs                                                       27.25-27.4  3.273-3.255                                                                              s                                                        30.05-30.25 2.974-2.955                                                                              m-s                                                      ______________________________________                                    

                  TABLE T                                                          ______________________________________                                         (ELAPSO-43)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         12.3-12.95  7.20-6.83 m-vs                                                     16.8-17.45  5.28-5.09 vw-w                                                     21.45-21.85 4.145-4.071                                                                              m-vs                                                     27.1-27.85  3.291-3.232                                                                              w-vs                                                     32.4-33.2   2.763-2.699                                                                              vw-m                                                     ______________________________________                                    

                  TABLE U                                                          ______________________________________                                         (ELAPSO-44)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.2-9.6     9.61-9.21 m-vs                                                     15.9-16.3   5.57-5.44 vw-m                                                     20.5-21.0   4.33-4.23 m-vs                                                     24.3-25.1    3.66-3.548                                                                              w-m                                                      30.5-31.1   2.931-2.876                                                                              vw-m                                                     ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         (ELAPSO-46)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         7.2-8.1     12.28-10.92                                                                              vs                                                       12.9-13.6   6.86-6.51 vw                                                       21.2-22.2    4.19-4.501                                                                              vw-m                                                      22.5-23.45  3.95-3.793                                                                              vw-m                                                     26.6-27.9   3.351-3.198                                                                              vw-m                                                     ______________________________________                                    

                  TABLE W                                                          ______________________________________                                         (ELAPSO-47)                                                                    2θ    d(Å)  Relative Intensity                                       ______________________________________                                         9.4-9.6     9.41-9.21 vs                                                       12.8-13.1   6.92-6.76 vw-m                                                     16.0-16.3   5.54-5.44 vw-m                                                     20.5-21.0   4.31-4.23 m-vs                                                     24.6-25.3   3.613-3.526                                                                              vs-m                                                     30.6-31.1   2.921-2.876                                                                              vw-m                                                     ______________________________________                                    

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

ELAPSO MOLECULAR SIEVE COMPOSITIONS

The ELAPSO molecular sieves of the invention may be prepared having one or more elements present as framework oxide units such that the ELAPSO molecular sieves contain framework oxide units "ELO₂ ", ALO₂ ⁻, PO₂ ⁺ and SiO₂ where "EL" denominates at least one element capable of forming a framework oxide unit with AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units. The following ELAPSO molecular sieves are representative of molecular sieves prepared according to the instant invention:

COBALT-ALUMINUM-PHOSPHORUS-SILICON-OXIDE MOLECULAR SIEVES

Molecular sieves containing cobalt, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents

In the following examples the CoAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isoproproxide;

(b) CATAPAL: Trademark of Condea Corporation for pseudoboehmite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) Co(Ac)₂ : cobalt acetate Co(C₂ H₃ O₂)₂.4H₂ O;

(e) CoSO₄ : cobalt sulfate (CoSO₄.7H₂ O);

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TBAOH: tetrabutylammonium hydroxide (25 wt % in methanol);

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex; cyclohexylamine;

(m) TEAOH; tetraethylammonium hydroxide (40 wt. % in water);

(n) DEEA: diethanolamine;

(o) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water); and

(p) TMAOH: tetramethylammonium hydroxide (40 wt. % in water)

Preparative Procedure

The CoAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:

    eR:fCoO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, h, i, g and j represent the moles of template R, cobalt (expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅), SiO₂ and H₂ O, respectively. The values for e, f, h, i, g and j were as set forth in the hereinafter discussed preparative examples.

The reaction mixtures were prepared by forming a starting reaction mixture comprising the H₃ PO₄ and one half of the water. This mixture was stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX-LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The cobalt source (Co(Ac)₂, Co(SO₄) or mixtures thereof) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C., 200° C. or 225° C.) for a time. Alternatively, if the digestion temperature was 100° C. the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

EXAMPLES 1A TO 31A

CoAPSO molecular sieves were prepared according to the above described procedure and the CoAPSO products determined by x-ray analysis. The results of examples 1A to 31A are set forth in Tables I-A and II-A. Tables I-A and II-A also contain examples AA to EA wherein X-ray analysis of the reaction mixture product did not show CoAPSO products.

In the Tables I-A and II-A, the reaction mixtures are described as the ratio of molar oxides:

    eR:fCoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :gSiO.sub.2 :50H.sub.2 O

where "e", "R", "f" and "g" are as above defined. Examples were prepared using this reaction mixture unless otherwise noted in Tables I-A to II-A. The values for "e", "f" and "g" are given in Tables I-A and II-A.

                                      TABLE I-A                                    __________________________________________________________________________     Example                                                                             Template                                                                            e f g Temp (°C.)                                                                    Time (days)                                                                           CoAPSO Product(s).sup.1                           __________________________________________________________________________     1A   Quin 1 0.2                                                                              0.2                                                                              150   4      CoAPSO-16;                                                                            CoAPSO-35                                  2A   Quin 1 0.2                                                                              0.2                                                                              150   10     CoAPSO-16:                                                                            CoAPSO-35                                  3A   Quin 1 0.2                                                                              0.2                                                                              200   4      CoAPSO-16;                                                                            CoAPSO-35                                  4A   Quin 1 0.2                                                                              0.2                                                                              200   10     CoAPSO-16;                                                                            CoAPSO-35                                  5A   Quin 1 0.2                                                                              0.2                                                                              100   4      CoAPSO-35;                                                                            CoAPSO-16                                  6A   Quin 1 0.2                                                                              0.2                                                                              100   10     CoAPSO-16;                                                                            CoAPSO-35                                  7A   MQuin                                                                               1 0.2                                                                              0.2                                                                              150   2      CoAPSO-35;                                                                            CoAPSO-17                                  8A   MQuin                                                                               1 0.2                                                                              0.2                                                                              150   7      CoAPSO-35.sup.                                    9A   MQuin                                                                               1 0.2                                                                              0.2                                                                              200   2      CoAPSO-35.sup.                                    10A  MQuin                                                                               1 0.2                                                                              0.2                                                                              200   7      CoAPSO-35.sup.                                     11A.sup.2,3                                                                        TBAOH                                                                               2 0.4                                                                              0.4                                                                              200   4      CoAPSO-36;                                                                            CoAPSO-5                                    12A.sup.2,3                                                                        TBAOH                                                                               2 0.4                                                                              0.4                                                                              200   10     CoAPSO-36;                                                                            CoAPSO-5                                   __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predominence in the product.                  .sup.2 The molar amount of Al.sub.2 O.sub.3 was 0.8 instead of 0.9.            .sup.3 Send crystals of CoAPO36 were employed in this examples, as             disclosed in U.S. Ser. No. 514,334, filed July 15, 1983.                 

                                      TABLE II-A                                   __________________________________________________________________________     Example                                                                             Template                                                                            e f g Temp (°C.)                                                                    Time (days)                                                                           CoAPSO Product(s).sup.1                           __________________________________________________________________________     13A  C-hex                                                                               1.0                                                                              0.2                                                                              0.6                                                                              150    4     CoAPSO-44;                                                                            CoAPSO-5                                                                CoAPSO-13.sup.                                    14A  C-hex                                                                               1.0                                                                              0.2                                                                              0.6                                                                              150   10     CoAPSO-44;                                                                            CoAPSO-5                                                                CoAPSO-13.sup.                                    15A  C-hex                                                                               1.0                                                                              0.2                                                                              0.6                                                                              200    4     CoAPSO-44.sup.                                    16A  C-hex                                                                               2.0                                                                              0.2                                                                              0.6                                                                              150    4     CoAPSO-44;                                                                            CoAPSO-13                                  17A  C-hex                                                                               2.0                                                                              0.2                                                                              0.6                                                                              150   10     CoAPSO-44;                                                                            CoAPSO-13                                  18A  C-hex                                                                               2.0                                                                              0.2                                                                              0.6                                                                              200    4     CoAPSO-44.sup.                                    19A  C-hex                                                                               2.0                                                                              0.2                                                                              0.6                                                                              200   10     CoAPSO-44.sup.                                    20A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              150    4     CoAPSO-5 .sup.                                    21A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              150   11     CoAPSO-5 .sup.                                    22A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              200    4     CoAPSO-5 .sup.                                    23A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              200   11     CoAPSO-5 .sup.                                    24A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              150    2     CoAPSO-5 .sup.                                    25A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              150   15     CoAPSO-5 .sup.                                    26A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              200     2    CoAPSO-5 .sup.                                    27A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              200   15     CoAPSO-5 .sup.                                    28A  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              150   21     CoAPSO-5                                          29A  Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.2                                                                              150    3     CoAPSO-5;                                                                             CoAPSO-36                                  30A  Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.2                                                                              150   10     CoAPSO-5;                                                                             CoAPSO-36                                  31A  Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.2                                                                              200    3     CoAPSO-5;                                                                             CoAPSO-36                                   AA* TBAOH                                                                               2.0                                                                              0.4                                                                              0.4                                                                              150    4     --                                                 BA* TBAOH                                                                               2.0                                                                              0.4                                                                              0.4                                                                              150   10     --                                                CA   Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              100    4     --                                                DA   Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              100   11     --                                                EA   Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.2                                                                              200   21     --                                                __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predominence in the product. A "--"           indicates that Xray analysis failed to show CoAPSO products.                   *The molar amount of Al.sub.2 O.sub.3 was 0.8 instead of 0.9.            

EXAMPLES 32A TO 61A

Examples 32A to 61A were carried out using di-n-propylamine as the organic templating agent. The preparative procedure was as above described except that in examples 39A to 45A and 53A to 61A the preparative procedure was modified such that the cobalt acetate was added to the phosphoric acid and water, followed by addition of the aluminum source, silicon source and then the organic templating agent. The aluminum source in examples 32A to 45A, 60A and 61A was aluminum isoproproxide and in examples 46A to 59A the aluminum source was CATAPAL. The reaction mixtures for examples 32A to 61A are described in terms of the molar oxide ratios: ePr₂ NH:0.2CoO:0.9Al₂ O₃ :0.9P₂ O₅ ;0.2SiO₂ :50H₂ O where "e" is the moles of template Pr₂ NH and where "e" was one (1) for examples 32A to 35A, 42A to 45A, 49A to 52A, 56A to 61A and "e" was two (2) for examples 36A to 41A, 46A to 48A, 53A to 55A. Examples FA, GA, HA and IA are reaction mixtures where X-ray analysis of the reaction products did not show CoAPSO products. Examples 32 to 61 and F, G, H, and I are set forth in Table III.

                                      TABLE III-A                                  __________________________________________________________________________     Example                                                                             Temp (°C.)                                                                    Time (days)                                                                           CoAPSO Product(s).sup.1                                      __________________________________________________________________________     32A  150    4     CoAPSO-11; CoAPSO-39                                         33A  150   11     CoAPSO-11; CoAPSO-46; CoAPSO-39                              34A  200    4     CoAPSO-11; CoAPSO-39; CoAPSO-46                              35A  200   11     CoAPSO-11; CoAPSO-39; CoAPSO-5                               36A  150   10     CoAPSO-46                                                    37A  200    4     CoAPSO-11; CoAPSO-5; CoAPSO-39                               38A  200   10     CoAPSO-11; CoAPSO-5                                          39A  150   10     CoAPSO-46                                                    40A  200    4     CoAPSO-11; CoAPSO-5; CoAPSO-39; CoAPSO-46                    41A  200   10     CoAPSO-11; CoAPSO-5; CoAPSO-39; CoAPSO-46                    42A  150    4     CoAPSO-11                                                    43A  150   11     CoAPSO-11; CoAPSO-46                                         44A  200    4     CoAPSO-11; CoAPSO-39                                         45A  200   11     CoAPSO-11; CoAPSO-39                                         46A  150    4     CoAPSO-46                                                    47A  150   10     CoAPSO-46; CoAPSO-11                                         48A  200    4     CoAPSO-46; CoAPSO-11                                         49A  150   10     CoAPSO-11                                                    50A  150    4     CoAPSO-11                                                    51A  200   10     CoAPSO-11                                                    52A  200    4     CoAPSO-11                                                    53A  150   10     CoAPSO-11; CoAPSO-46                                         54A  200    4     CoAPSO-46; CoAPSO-11; CoAPSO-20                              55A  200   10     CoAPSO-46; CoAPSO-11; CoAPSO-20                              56A  150    4     CoAPSO-11                                                    57A  150   10     CoAPSO-11                                                    58A  200    4     CoAPSO-11                                                    59A  200   10     CoAPSO-11                                                    60A  150    4     CoAPSO-11                                                    61A  150    4     CoAPSO-11                                                    FA   100    4       --                                                         GA   100   11       --                                                         HA   150     4      --                                                         IA   150    4       --                                                         __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predominence in the product. A "--"           indicates that Xray analysis failed to show CoAPSO products.             

EXAMPLES 62A to 83A

Examples 62A to 83A were carried out according to the preparative procedure employed in examples 1A to 31A except that the organic templating agent was as TEAOH (tetraethylammonium hydroxide). The reaction mixtures for examples 62A to 83A were:

    1.0TEAOH:fCoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :gSiO.sub.2 :5OH.sub.2 O

wherein "f" was 0.2 except that "f" was 0.1 for examples 78A to 79A and was 0.05 for examples 80A to 83A; and g was 0.2 for examples 62A to 70A and was 0.6 for examples 71A to 83A. The reactive cobalt source was cobalt (II) sulfate for examples 62A to 70A and cobalt (II) acetate for examples 71A to 83A.

The results of examples 62A to 83A are set forth in Table IV-A.

                  TABLE IV-A                                                       ______________________________________                                         Example Temp (°C.)                                                                        Time (days)                                                                               CoAPSO Product(s).sup.1                           ______________________________________                                         62A     150        4         CoAPSO-34; CoAPSO-5                               63A     150       12         CoAPSO-34; CoAPSO-5                               64A     150       12         CoAPSO-34                                         65A     200        4         CoAPSO-34; CoAPSO-5                               66A     200       12         CoAPSO-5; CoAPSO-34                               67A     200       12         CoAPSO-34                                         68A     100        4         CoAPSO-34                                         69A     100       12         CoAPSO-34                                         70A     100       12         CoAPSO-34                                         71A     100        2         CoAPSO-34                                         72A     100        7         CoAPSO-34                                         73A     150        2         CoAPSO-34; CoAPSO-5                               74A     150       13         CoAPSO-34; CoAPSO-5                               75A     200        2         CoAPSO-5; CoAPSO-34                               76A     200        7         CoAPSO-5; CoAPSO-34                               77A     100       14         CoAPSO-34                                         78A     100       14         CoAPSO-34                                         79A     100       28         CoAPSO-34                                         80A     100       10         CoAPSO-34                                         81A     100       20         CoAPSO-34                                         82A     100        2         CoAPSO-34                                         83A     100        4         CoAPSO-34                                         ______________________________________                                          .sup.1 Major species as indentified by Xray powder diffraction pattern of      product, except that when two or more species were identified the species      are listed in the order of their predominance in the product.            

EXAMPLES 84A TO 106A

Examples 84A to 106A were carried out according to the preparative procedure employed in examples 1A to 31A except the organic template was as is shown in Table V-A. The reaction mixture was:

    eR:f5CoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :0.6SiO.sub.2 :50H.sub.2 O

where "e" was one (1) except that "e" was 1.5 for examples 94A to 97A and "e" was 2.0 for example 104A. The results of examples 84A to 106A are set forth in Table V-A.

                                      TABLE V-A                                    __________________________________________________________________________     Example                                                                             Template                                                                            e f   Temp (°C.)                                                                    Time (days)                                                                           CoAPSO Product(s).sup.1                           __________________________________________________________________________     84A  TEAOH                                                                               1.0                                                                               0.025                                                                             125   3      CoAPSO-34; CoAPSO-18;                             85A  TEAOH                                                                               1.0                                                                               0.025                                                                             125   5      CoAPSO-34; CoAPSO-5;                              86A  TEAOH                                                                               1.0                                                                               0.025                                                                             100   5      CoAPSO-34; CoAPSO-5;                              87A  TEAOH                                                                               1.0                                                                               0.025                                                                             100   5      CoAPSO-34;                                        88A  TEAOH                                                                               1.0                                                                               0.025                                                                             100   3      CoAPSO-34;                                        89A  TEAOH                                                                               1.0                                                                               0.025                                                                             100   5      CoAPSO-34;                                        90A  TEAOH                                                                               1.0                                                                               0.025                                                                             100   7      CoAPSO-34;                                        91A  Quin 1.0                                                                              0.2 225   5      CoAPSO-35; CoAPSO-16                              92A  C-hex                                                                               1.0                                                                              0.2 225   5      CoAPSO-5; CoAPSO-44                               .sup. 93A.sup.2                                                                     Pr.sub.3 N                                                                          1.5                                                                              0.2 150   2      CoAPSO-36;                                        .sup. 94A.sup.2                                                                     Pr.sub.3 N                                                                          1.5                                                                              0.2 150   7      CoAPSO-36;                                        .sup. 95A.sup.2                                                                     Pr.sub.3 N                                                                          1.5                                                                              0.2 200   2      CoAPSO-36; CoAPSO-5                               .sup. 96A.sup.2                                                                     Pr.sub.3 N                                                                          1.5                                                                              0.2 200   7      CoAPSO-36; CoAPSO-5                               .sup. 97A.sup.3                                                                     Pr.sub.2 NH                                                                         1.0                                                                              0.2 150   4      CoAPSO-31; CoAPSO-11                              .sup. 98A.sup.3                                                                     Pr.sub.2 NH                                                                         1.0                                                                              0.2 150   10     CoAPSO-46; CoAPSO-31                              .sup. 99A.sup.3                                                                     Pr.sub.2 NH                                                                         1.0                                                                              0.2 200   4      CoAPSO-31; CoAPSO-11                              100A.sup.3                                                                          Pr.sub.2 NH                                                                         1.0                                                                              0.2 200   10     CoAPSO-31; CoAPSO-11;                                                          CoAPSO-5; CoAPSO-46                               101A.sup.3                                                                          Pr.sub.2 NH                                                                         1.0                                                                              0.2 150   2      CoAPSO-31                                         102A.sup.3                                                                          Pr.sub.2 NH                                                                         1.0                                                                              0.2 150   3      CoAPSO-31                                         103A.sup.3                                                                          Pr.sub.2 NH                                                                         1.0                                                                              0.2 200   2      CoAPSO-31; CoAPSO-46                              104A DEEA 2.0                                                                              0.2 150   2      CoAPSO-47                                         105A TMAOH                                                                               1.0                                                                              0.2 150   4      CoAPSO-20                                         106A TMAOH                                                                               1.0                                                                              0.2 200   4      CoAPSO-20                                         __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the spaces       are listed in the order of their predominance in the product.                  .sup.2 Seed crystals of CoAPO36 were employed (copending U.S. Ser. No.         514,334, filed July 15, 1983).                                                 .sup.3 Seed crystals of AlPO.sub.4 -31 (U.S. Pat. No. 4,310,440) were          employed.                                                                

EXAMPLE 107A

Samples of the products were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the CoAPSO was prepared being given in parenthesis after the designation of the CoAPSO species.

(a) The chemical analysis for CoAPSO-11 (example 35A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.1                                                             P.sub.2 O.sub.5                                                                              46.1                                                             CoO           6.4                                                              SiO.sub.2     3.5                                                              Carbon        5.2                                                              LOI*          11.7                                                             ______________________________________                                          *LOI = Loss on Ingnition                                                 

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.085 CoO; 0.305 Al₂ O₃ : 0.325 P₂ O₅ :0.058SiO₂ ; and a formula (anhydrous basis) of:

    0.07R(Co.sub.0.06 Al.sub.0.47 P.sub.0.46 Si.sub.0.04)O.sub.2

(b) The chemical analysis for CoAPSO-11 (example 42A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.5                                                             P.sub.2 O.sub.5                                                                              44.7                                                             CoO           4.4                                                              SiO.sub.2     1.4                                                              Carbon        3.9                                                              LOI*          15.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.059 CoO; 0.319 Al₂ O₃ : 0.315 P₂ O₅ : 0.023 SiO₂ ; and a formula (anhydrous basis) of:

    0.05R(Co.sub.0.04 Al.sub.0.47 P.sub.0.47 Si.sub.0.02)O.sub.2

(c) The chemical analysis for CoAPSO-20 (example 106A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.7                                                             P.sub.2 O.sub.5                                                                              37.8                                                             CoO           4.6                                                              SiO.sub.2     10.0                                                             Carbon        9.4                                                              LOI*          18.4                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.061 CoO; 0.272 Al₂ O₃ : 0.266 P₂ O₅ : 0.166 SiO₂ ; and a formula (anhydrous basis) of:

    0.20R(Co.sub.0.05 Al.sub.0.42 P.sub.0.41 Si.sub.0.13)O.sub.2

(d) The chemical analysis of CoAPSO-31 (example 101A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.3                                                             P.sub.2 O.sub.5                                                                              42.4                                                             CoO           4.3                                                              SiO.sub.2     3.8                                                              Carbon        2.8                                                              LOI*          16.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.057 CoO; 0.317 Al₂ O₃ : 0.299 P₂ O₅ : 0.063 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R(Co.sub.0.04 Al.sub.0.47 P.sub.0.44 Si.sub.0.05)O.sub.2

(e) The chemical analysis for CoAPSO-34 (example 69A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             28.2                                                             P.sub.2 O.sub.5                                                                              41.7                                                             CoO           4.7                                                              SiO.sub.2     1.1                                                              Carbon        5.9                                                              LOI*          23.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.063 CoO; 0.277 Al₂ O₃ : 0.294 P₂ O₅ : 0.018 SiO₂ ; and a formula (anhydrous basis) of:

    0.06R(Co.sub.0.05 Al.sub.0.45 P.sub.0.48 Si.sub.0.02)O.sub.2

(f) The chemical analysis of CoAPSO-34 (example 72A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             28.4                                                             P.sub.2 O.sub.5                                                                              40.6                                                             CoO           4.6                                                              SiO.sub.2     2.2                                                              Carbon        7.8                                                              LOI*          23.3                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.061 CoO; 0.279 Al₂ O₃ : 0.282 P₂ O₅ : 0.037 SiO₂ ; and a formula (anhydrous basis) of:

    0.08R(Co.sub.0.05 Al.sub.0.46 P.sub.0.46 Si.sub.0.03)O.sub.2

(g) The chemical analysis for CoAPSO-34 (example 79A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.7                                                             P.sub.2 O.sub.5                                                                              40.5                                                             CoO           2.5                                                              SiO.sub.2     3.4                                                              Carbon        8.4                                                              LOI*          20.8                                                             ______________________________________                                          LOI* = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.033 CoO:0.311 Al₂ O₃ : 0.285 P₂ O₅ : 0.057 SiO₂ ; and a formula (anhydrous basis) of:

    0.09R(Co.sub.0.03 Al.sub.0.49 P.sub.0.45 Si.sub.0.05)O.sub.2

(h) The chemical analysis of CoAPSO-34 (example 81A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.0                                                             P.sub.2 O.sub.5                                                                              39.6                                                             CoO           1.2                                                              SiO.sub.2     2.7                                                              Carbon        6.4                                                              LOI*          22.8                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.016 CoO; 0.314 Al₂ O₃ : 0.279 P₂ O₅ : 0.045 SiO₂ ; and a formula (anhydrous basis) of:

    0.07R(Co.sub.0.01 Al.sub.0.50 P.sub.0.45 Si.sub.0.04)O.sub.2

(i) The chemical analysis of CoAPSO-34 (example 83A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             33.8                                                             P.sub.2 O.sub.5                                                                              40.6                                                             CoO           1.6                                                              SiO.sub.2     2.1                                                              Carbon        6.6                                                              LOI*          21.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:

    0.021 CoO:0.332Al.sub.2 O.sub.3 :0.286 P.sub.2 O.sub.5 :0.035SiO.sub.2 ;

and a formula (anhydrous basis) of:

    0.07R(Co.sub.0.02 Al.sub.0.53 P.sub.0.46 Si.sub.0.03)O.sub.2

(j) The chemical analysis of CoAPSO-34 (example 77A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             30.1                                                             P.sub.2 O.sub.5                                                                              41.7                                                             CoO           4.8                                                              SiO.sub.2     2.6                                                              Carbon        9.0                                                              LOI*          19.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.064 CoO; 0.295 Al₂ O₃ : 0.294 P₂ O₅ : 0.043 SiO₂ ; and a formula (anhydrous basis) of:

    0.09R(Co.sub.0.05 Al.sub.0.46 P.sub.0.46 Si.sub.0.03)O.sub.2

(k) The chemical analysis of CoAPSO-34 (example 89A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.8                                                             P.sub.2 O.sub.5                                                                              38.8                                                             CoO           0.71                                                             SiO.sub.2     2.2                                                              Carbon        6.6                                                              LOI*          24.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.01 CoO; 0.312 Al₂ O₃ : 0.273 P₂ O₅ : 0.037 SiO₂ ; and a formula (anhydrous basis) of:

    0.07R(Co.sub.0.01 Al.sub.0.51 P.sub.0.45 Si.sub.0.03)O.sub.2

where the value for cobalt is rounded off from 0.008.

(1) The chemical analysis of CoAPSO-34 (example 90A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.4                                                             P.sub.2 O.sub.5                                                                              39.3                                                             CoO           0.66                                                             SiO.sub.2     3.5                                                              Carbon        7.2                                                              LOI*          23.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.009 CoO; 0.318 Al₂ O₃ : 0.277 P₂ O₅ : 0.058 SiO₂ ; and a formula (anhydrous basis) of:

    0.08R(Co.sub.0.01 Al.sub.0.51 P.sub.0.44 Si.sub.0.05)O.sub.2

where the value for cobalt is rounded off from 0.007.

(m) The chemical analysis of CoAPSO-35 (example 10A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.0                                                             P.sub.2 O.sub.5                                                                              41.6                                                             CoO           4.3                                                              SiO.sub.2     4.3                                                              Carbon        13.0                                                             LOI*          22.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.057 CoO; 0.265 Al₂ O₃ : 0.290 P₂ O₅ : 0.054 SiO₂ ; and a formula (anhydrous basis) of:

    0.14R(Co.sub.0.05 Al.sub.0.43 P.sub.0.48 Si.sub.0.04)O.sub.2

(n) The chemical analysis of CoAPSO-36 (example 93A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             29.5                                                             P.sub.2 O.sub.5                                                                              39.6                                                             CoO           5.2                                                              SiO.sub.2     6.6                                                              Carbon        3.3                                                              LOI*          18.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.069 CoO; 0.289 Al₂ O₃ : 0.279 P₂ O₅ : 0.110 SiO₂ ; and a formula (anhydrous basis) of:

    0.03R(Co.sub.0.05 Al.sub.0.44 P.sub.0.42 Si.sub.0.08)O.sub.2

(o) The chemical analysis of CoAPSO-44 (example 19A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             26.3                                                             P.sub.2 O.sub.5                                                                              36.3                                                             CoO           4.5                                                              SiO.sub.2     10.0                                                             Carbon        13.2                                                             LOI*          22.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.06 CoO; 0.258 Al₂ O₃ : 0.256 P₂ O₅ : 0.166 SiO₂ ; and a formula (anhydrous basis) of:

    0.18R(Co.sub.0.05 Al.sub.0.41 P.sub.0.41 Si.sub.0.13)O.sub.2

(p) The chemical analysis of CoAPSO-46 (example 36A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.4                                                             P.sub.2 O.sub.5                                                                              31.5                                                             CoO           6.2                                                              SiO.sub.2     2.9                                                              Carbon        4.2                                                              LOI*          27.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.08 CoO; 0.31 Al₂ O₃ : 0.22 P₂ O₅ : 0.05 SiO₂ ; and a formula (anhydrous basis) of:

    0.06R(Co.sub.0.07 Al.sub.0.52 P.sub.0.37 Si.sub.0.04)O.sub.2

(q) The chemical analysis of CoAPSO-47 (example 104A) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             22.7                                                             P.sub.2 O.sub.5                                                                              39.8                                                             CoO           8.2                                                              SiO.sub.2     2.9                                                              Carbon        11.4                                                             LOI*          25.2                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.109 CoO; 0.223 Al₂ O₃ : 0.280 P₂ O₅ : 0.048 SiO₂ ; and a formula (anhydrous basis) of:

    0.16R(Co.sub.0.09 Al.sub.0.38 P.sub.0.48 Si.sub.0.04)O.sub.2

EXAMPLE 108A

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of CoAPSO products. Analysis of crystals having a morphology characteristic of the CoAPSO compositions noted hereinafter gave the following analysis based on relative peak heights:

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         (a) CoAPSO-11 (example 42A):                                                   Co        1.0                                                                  Al        8.0                                                                  P         10.0                                                                 Si        1.0                                                                  (b) CoAPSO-20 (example 106A):                                                  Co        0.5                                                                  Al        8.0                                                                  P         7.5                                                                  Si        3.4                                                                  (c) CoAPSO-34 (example 69A):                                                   Co        0.5                                                                  Al        8.0                                                                  P         10.0                                                                 Si        1.0                                                                  (d) CoAPSO-35 (example 10A):                                                   Co        0.5                                                                  Al        9.0                                                                  P         7.5                                                                  Si        1.0                                                                  (e) CoAPSO-36 (example 95A):                                                   Co        0.6                                                                  Al        9.1                                                                  P         9.4                                                                  Si        2.2                                                                  (f) CoAPSO-44 (example 16A):                                                   Co        1.0                                                                  Al        8.0                                                                  P         8.0                                                                  Si        0.6                                                                  (g) CoAPSO-47 (example 104A):                                                  Co        0.7                                                                  Al        8.4                                                                  P         9.2                                                                  Si        2.8                                                                  ______________________________________                                    

EXAMPLE 109A

Samples of the CoAPSO products were tested for adsorption capacities. The CoAPSO products were evaluated either in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined CoAPSO products were:

    ______________________________________                                         (a) CoAPSO-11 (example 61A):                                                             Kinetic   Pressure   Temp  Wt. %                                     Adsorbate Diameter,Å                                                                           (Torr)     (°C.)                                                                         Adsorbed*                                 ______________________________________                                         O.sub.2   3.46      106        -183  6.9                                       O.sub.2   3.46      744        -183  12.1                                      isobutane 5.0       740        24.2  3.9                                       cyclo-hexane                                                                             6.0        82        23.9  13.5                                      neopentane                                                                               6.2       74l        25.3  3.6                                       H.sub.2 O 2.65      4.6        24.9  7.1                                       H.sub.2 O 2.65       19        24.8  21.0                                      ______________________________________                                          *calcined in air at 600° C. for 1 hour prior to activation        

The above data demonstrate that the pore size of the calcined product is about 6.0 Å.

    ______________________________________                                         (b) CoAPSO-20 (example 106A)                                                           Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2 3.46       102       -183    5                                         O.sub.2 3.46       744       -183    6.4                                       H.sub.2 O                                                                              2.65       4.6       23.3    10                                        H.sub.2 O                                                                              2.65       19        23.2    14                                        ______________________________________                                          *calcined in air at 500° C. for one hour prior to activation.     

The above data demonstrate that the pore size of the calcined product is about 3.0 Å.

    ______________________________________                                         (c) CoAPSO-31 (example 102A)                                                           Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2 3.46       105       -183    6.9                                       O.sub.2 3.46       741       -183    12.8                                      neopentane                                                                             6.2        739       23.5    5.8                                       H.sub.2 O                                                                              2.65       4.6       23.5    5.8                                       H.sub.2 O                                                                              2.65       20        24.0    15.9                                      ______________________________________                                          *calcined in air at 500° C. for 1.5 hrs prior to activation.      

The above data demonstrate that the pore size of the calcined product is greater than about 6.2 Å.

    ______________________________________                                         (d) CoAPSO-34 (example 78A)                                                            Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2 3.46       103       -183    15.9                                      O.sub.2 3.46       731       -183    28.2                                      n-hexane                                                                               4.3        103       23.9    9.8                                       isobutane                                                                              5.0        741       23.3    1.8                                       H.sub.2 O                                                                              2.65       4.6       23.8    11.3                                      H.sub.2 O                                                                              2.65       18.5      24.0    28.9                                      ______________________________________                                          *calcined in nitrogen at 425° C. for 2 hrs prior to activation.   

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

    ______________________________________                                                 Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         (e) CoAPSO-34 (example 89A)                                                    O.sub.2 3.46       105       -183    18.6                                      O.sub.2 3.46       741       -183    28.8                                      isobutane                                                                              5.0        108       23.9    9.9                                       n-hexane                                                                               4.3        742       23.3    1.2                                       H.sub.2 O                                                                              2.65       4.6       23.8    10.7                                      H.sub.2 O                                                                              2.65       20.0      24.0    30.1                                      ______________________________________                                          *calcined in air at 600° C. for one hour prior to activation.     

    (f) CoAPSO-35 (example 8A)                                                     ______________________________________                                         O.sub.2 3.46       103       -183    11.7                                      O.sub.2 3.46       731       -183    15.5                                      isobutane                                                                              5.0        741       24.5    0.6                                       n-hexane                                                                               4.3        103       24.4    3.5                                       H.sub.2 O                                                                              2.65       4.6       24.4    14.3                                      H.sub.2 O                                                                              2.65       18.5      23.9    22.7                                      ______________________________________                                          *calcined in nitrogen at 500° C. for 2.0 hours prior to activation                                                                               

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

    ______________________________________                                         (g) CoAPSO-44 (example 19A)                                                            Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2 3.46       103       -183    24.8                                      O.sub.2 3.46       731       -183    31.4                                      n-hexane                                                                               4.3        103       24.4    7.4                                       isobutane                                                                              5.0        741       24.5    0.3                                       H.sub.2 O                                                                              2.65       4.6       24.4    27.8                                      H.sub.2 O                                                                              2.65       18.5      23.9    35.1                                      ______________________________________                                          *calcined in air at 500° C. for 1.25 hrs. prior to activation.    

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

    ______________________________________                                         (h) CoAPSO-47 (example 104A)                                                           Kinetic    Pressure  Temp    Wt. %                                     Adsorbate                                                                              Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2 3.46       102       -183    4.1                                       O.sub.2 3.46       744       -183    4.9                                       isobutane                                                                              5.0        746       24.1    0.6                                       n-hexane                                                                               4.3        95        23.6    1.3                                       H.sub.2 O                                                                              2.65       4.6       23.3    9.6                                       H.sub.2 O                                                                              2.65       19        23.2    14.3                                      ______________________________________                                          *calcined in air at 500° C. for 1.5 hrs. prior to activation.     

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

EXAMPLE 110A

(a) The as-synthesized CoAPSO-5 of example 76A was subjected to analysis by x-ray. The CoAPSO-5 product was characterized by the x-ray powder diffraction pattern of Table VII-A below:

                  TABLE VII-A                                                      ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         7.4            11.95   100                                                     9.6*           9.21    65                                                      12.9**         6.86    19                                                      14.1*          6.28    10                                                      14.9           5.95    26                                                      16.0*          5.54    32                                                      17.8*          4.98    13                                                      19.8           4.48    61                                                      20.5*          4.33    55                                                      21.1           4.21    74                                                      22.4**         3.97    94                                                      23.0*          3.87    10                                                      24.8           3.59    16                                                      25.2*          3.53    16                                                      26.0**         3.427   42                                                      27.4*          3.255   13                                                      28.2*          3.164   10                                                      29.1           3.069   19                                                      29.5*          3.028   10                                                      30.1           2.969   29                                                      30.6*          2.921   23                                                      31.1*          2.876   19                                                      33.7**         2.660   10                                                      34.5**         2.600   19                                                      37.0           2.430    7                                                      37.7           2.386   16                                                      41.5           2.176    7                                                      42.2           2.141    8                                                      43.7           2.071    7                                                      44.9**         2.019    7                                                      47.8**         1.903   10                                                      48.9*          1.863   10                                                      55.8           1.647   10                                                      ______________________________________                                          *peak resulting from CoAPSO34                                                  **peak resulting from CoAPSO34 and CoAPSO5                               

(b) CoAPSO-5, of example 21A was calcined in air at 600° for four hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table VIII-A below:

                  TABLE VIII-A                                                     ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                         7.4            11.95   100                                                     12.9           6.86    22                                                      14.8           5.99    13                                                      19.7           4.51    39                                                      20.3*          4.37    83                                                      21.0           4.23    74                                                      21.4*          4.15    99                                                      22.4           3.97    74                                                      22.9*          3.88    35                                                      24.4           3.65    13                                                      25.9           3.440   30                                                      27.1**         3.290   17                                                      28.1*          3.175   26                                                      29.0           3.079   26                                                      30.1           2.969   30                                                      33.7           2.660   13                                                      34.6           2.592   22                                                      35.6*          2.522   26                                                      37.0           2.430   13                                                      37.8           2.380   13                                                      42.8           2.113   13                                                      43.8           2.067    9                                                      47.8           1.903    9                                                      55.8           1.647    9                                                      ______________________________________                                          *peak from tridynite                                                           **impurity peak                                                          

(c) The species denominated herein as CoAPSO-5 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" are the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-A:

                  TABLE IX-A                                                       ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         7.3-7.5     12.11-11.79                                                                              m-vs                                                     14.7-14.9   6.03-5.95 w-m                                                      19.6-19.8   4.53-4.48 w-m                                                      20.9-21.2   4.25-4.19 w-vs                                                     22.3-22.4   3.99-3.97 m-vs                                                     25.8-26.0   3.453-3.427                                                                              vw-m                                                     ______________________________________                                    

(d) The CoAPSO-5 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table X-A:

                  TABLE X-A                                                        ______________________________________                                         2θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         7.3-7.5       12.11-11.79                                                                              32-100                                                 12.7-12.9     6.97-6.86 2-22                                                   14.7-14.9     6.03-5.95 10-26                                                  19.6-19.8     4.53-4.48 7-39                                                   20.9-21.2     4.25-4.19 19-100                                                 22.3-22.4     3.99-3.97 25-94                                                  24.4-24.8     3.65-3.59 2-16                                                   25.8-26.0     3.453-3.427                                                                              6-41                                                   29.0-29.1     3.079-3.069                                                                              3-26                                                   29.9-30.1     2.988-2.969                                                                              3-30                                                   33.5-33.7     2.667-2.660                                                                              2-13                                                   34.4-34.6     2.607-2.592                                                                              4-22                                                   36.8-37.0     2.442-2.430                                                                              2-13                                                   37.5-37.8     2.398-2.380                                                                              3-16                                                   41.4-41.5     2.181-2.176                                                                              1-7                                                    42.2-42.8     2.141-2.113                                                                              1-13                                                   43.7-43.8     2.071-2.067                                                                              0-9                                                    44.9-45.0     2.019-2.014                                                                              1-7                                                    47.5-47.8     1.914-1.903                                                                              3-10                                                   55.6-55.8     1.653-1.647                                                                              1-10                                                   ______________________________________                                    

EXAMPLE 111A

(a) The as-synthesized CoAPSO-11 of example 42A was subjected to analysis by x-ray. The CoAPSO-11 product was characterized by the x-ray powder diffraction pattern of Table XI-A below:

                  TABLE XI-A                                                       ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         7.9            11.19   32                                                      9.3            9.51    72                                                      12.3*          7.20    16                                                      13.1           6.76    24                                                      15.6           5.68    32                                                      16.2           5.47    12                                                      18.2           4.87    16                                                      18.9           4.70    12                                                      20.3           4.37    40                                                      21.0           4.23    100                                                     22.1           4.02    56                                                      22.5           3.95    60                                                      22.7           3.92    72                                                      23.1           3.85    68                                                      24.6           3.62    20                                                      26.3           3.389   28                                                      28.2           3.164   16                                                      28.5           3.132   24                                                      29.4           3.038   20                                                      29.6           3.018   16                                                      29.9           2.988   16                                                      31.3           2.858   16                                                      32.6           2.747   24                                                      34.0           2.637   16                                                      36.3           2.475   12                                                      37.6           2.392   20                                                      39.3           2.292   12                                                      42.8           2.113    8                                                      44.8           2.023    8                                                      50.5           1.807   12                                                      54.4           1.687   12                                                      ______________________________________                                          *peak may contain impurity                                               

(b) CoAPSO-11, of example 42A was calcined in air at 600° for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XII-A below:

                  TABLE XII-A                                                      ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         8.1            10.92   70                                                      9.5            9.31    83                                                      13.1           6.76    26                                                      13.5           6.56    30                                                      15.8           5.61    56                                                      18.5*          4.80    17                                                      19.2           4.62    13                                                      20.2           4.40    sh                                                      20.3           4.37    35                                                      21.3           4.17    100                                                     22.3           3.99    61                                                      22.5           3.95    sh                                                      23.0           3.87    65                                                      23.4           3.80    52                                                      24.3           3.66    17                                                      25.1           3.548   17                                                      26.5           3.363   30                                                      26.6           3.351   sh                                                      28.2           3.164   13                                                      28.9           3.089   26                                                      29.5           3.028   17                                                      30.1           2.969   13                                                      30.5           2.931   17                                                      31.8           2.814   17                                                      32.9           2.722   22                                                      34.7           2.585   13                                                      36.2           2.481   13                                                      37.9           2.374   17                                                      38.3           2.350   17                                                      39.5           2.281    9                                                      ______________________________________                                          *peak may contain impurity                                               

(c) The species denominated herein as CoAPSO-11 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-A:

                  TABLE XIII-A                                                     ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         7.9-8.1     11.19-10.92                                                                              m                                                        9.3-9.5     9.51-9.31 m-s                                                      21.0-21.3   4.23-4.17 vs                                                       22.1-22.3   4.02-3.99 m                                                        22.7-23.1   3.92-3.85 m                                                        23.2-23.4   3.83-3.80 m                                                        ______________________________________                                    

(d) The CoAPSO-11 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XIV-A:

                  TABLE XIV-A                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         7.9-8.1       11.19-10.92                                                                              32-70                                                  9.3-9.5       9.51-9.31 72-83                                                  12.3*         7.20      16                                                     13.1-13.2     6.76-6.71 16-26                                                  13.5-13.6     6.56-6.51 30                                                     15.6-15.8     5.68-5.61 32-56                                                  16.2-16.3     5.47-5.44  8-12                                                  18.2-18.5     4.87-4.80 16-17                                                  18.9-19.2     4.70-4.62 12-13                                                  19.7-20.2     4.51-4.40 sh                                                     20.3          4.37      35-40                                                  21.0-21.3     4.23-4.17 100                                                    22.1-22.3     4.02-3.99 56-61                                                  22.4-22.6     3.97-3.93 sh-60                                                  22.7-23.1     3.92-3.85 65-72                                                  23.2-23.4     3.83-3.80 52-68                                                  24.3-24.6     3.66-3.62 17-20                                                  25.1          3.548     17                                                     26.3-26.5     3.389-3.363                                                                              28-30                                                  26.6          3.351     sh                                                     28.1-28.2     3.175-3.164                                                                              13-16                                                  28.5-28.9     3.132-3.089                                                                              24-26                                                  29.4-29.5     3.038-3.028                                                                              17-20                                                  29.6-30.5     3.018-2.931                                                                              13-17                                                  31.3-31.8     2.858-2.814                                                                              16-17                                                  32.6-32.9     2.747-2.722                                                                              22-24                                                  34.0-34.7     2.637-2.585                                                                              13-16                                                  36.2-36.3     2.481-2.475                                                                              12-13                                                  36.7-37.9     2.392-2.374                                                                              17-20                                                  38.3-38.4     2.350-2.344                                                                              17-18                                                  39.3-39.5     2.292-2.281                                                                               9-12                                                  42.8-42.9     2.113-2.108                                                                              8-9                                                    44.7- 44.8    2.027-2.023                                                                              8-9                                                    50.5-50.6     1.807-1.804                                                                               9-12                                                  54.4-54.6     1.687-1.681                                                                               9-12                                                  ______________________________________                                          *peak may contain impurity                                               

EXAMPLE 112-A

(a) The as-synthesized CoAPSO-16 of example 4A was subjected to analysis by x-ray. The CoAPSO-16 product was characterized by the x-ray powder diffraction pattern of Table XV-A below:

                  TABLE XV-A                                                       ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.7*          10.16     17                                                     11.0*         8.04      40                                                     11.5          7.69      32                                                     13.0*         6.81      15                                                     15.9*         5.57      13                                                     17.3*         5.13      55                                                     17.9*         4.96      13                                                     18.8          4.72      23                                                     20.8*         4.27      (sh)                                                   21.2*         4.19      40                                                     22.0**        4.04      100                                                    23.2**        3.83      21                                                     23.8*         3.74      11                                                     25.1*         3.548      9                                                     26.9**        3.314     23                                                     28.6*         3.121     26                                                     28.8*         3.100     26                                                     29.0          3.079     15                                                     29.6          3.018     11                                                     29.9          2.988     15                                                     32.2*         2.780     34                                                     32.8          2.730      9                                                     34.6**        2.592     13                                                     35.8*         2.508     11                                                     37.9          2.374      9                                                     40.1          2.249      9                                                     42.2*         2.141     11                                                     43.0*         2.103      9                                                     44.5          2.036      9                                                     48.6**        1.873     13                                                     49.6          1.838     11                                                     51.6          1.771     11                                                     52.6          1.740      6                                                     55.0          1.670      6                                                     55.4*         1.658     11                                                     ______________________________________                                          *peak resulting from CoAPSO35                                                  **peak resulting from CoAPSO16 and CoAPSO35                              

(b) The species denominated herein as CoAPSO-16 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVI-A:

                  TABLE XVI-A                                                      ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         11.4-11.6   7.76-7.63 w-s                                                      17.2-17.4   5.16-5.10 m                                                        18.7-18.9   4.75-4.70 vw-m                                                     21.9-22.1   4.06-4.02 vs                                                       23.1-23.3   3.85-3.82 m                                                        26.8-27.0   3.326-3.302                                                                              m                                                        29.8-29.9   2.998-2.988                                                                              w-m                                                      ______________________________________                                    

(c) The CoAPSO-16 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XVII-A:

                  TABLE XVII-A                                                     ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         11.4-11.6     7.76-763  11-79                                                  17.2-17.4     5.16-5.10 66-80                                                  18.7-18.9     4.75-4.70  7-53                                                  21.9-22.1     4.06-4.02 100                                                    23.1-23.3     3.85-3.82 21-24                                                  26.8-27.0     3.326-3.302                                                                              23-28                                                  29.0          3.079     14-18                                                  29.5-29.7     3.028-3.008                                                                               4-15                                                  29.8-29.9     2.998-2.988                                                                              15-29                                                  32.7-32.9     2.739-2.722                                                                              3-9                                                    34.5-34.7     2.600-2.585                                                                               9-13                                                  37.8-38.0     2.380-2.368                                                                              6-9                                                    40.0-40.2     2.534-2.243                                                                              1-9                                                    44.3-44.6     2.045-2.032                                                                              2-9                                                    48.5-48.7     1.877-1.870                                                                               8-13                                                  49.5-49.7     1.841-1.834                                                                               8-11                                                  51.5-51.7     1.774-1.768                                                                               6-11                                                  52.5-52.7     1.743-1.737                                                                              6-7                                                    54.9-55.1     1.672-1.667                                                                              1-6                                                    ______________________________________                                    

EXAMPLE 113A

(a) The as-synthesized CoAPSO-20 of example 106A was subjected to analysis by x-ray. The CoAPSO-20 product was characterized by the x-ray powder diffraction pattern of Table XVIII-A below:

                  TABLE XVIII-A                                                    ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         10.293        8.5942    7                                                      12.078        7.3278    1                                                      13.925        6.3595    46                                                     14.376        6.1609    2                                                      18.773        4.7268    2                                                      19.738        4.4977    42                                                     20.507        4.3307    3                                                      22.093        4.0233    3                                                      24.227        3.6735    100                                                    26.363        3.3806    3                                                      26.941        3.3094    3                                                      28.052        3.1808    11                                                     31.442        2.8451    11                                                     31.759        2.8175    2                                                      31.980        2.7985    2                                                      34.523        2.5980    16                                                     37.426        2.4029    1                                                      40.075        2.2499    4                                                      42.614        2.1215    4                                                      47.3          1.922     4                                                      51.8          1.765     8                                                      ______________________________________                                    

(b) CoAPSO-20, of example 106A was calcined in air at 500° for one hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XIX-A below:

                  TABLE XIX-A                                                      ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          10.6*         8.39    7                                                        21.1*         7.30    3                                                        12.2*         7.24    2                                                       14.0           6.33    75                                                       14.8*         6.01    3                                                        16.1*         5.51    2                                                       19.8           4.48    38                                                      22.2           4.01    4                                                       24.3           3.66    100                                                      26.7*         3.344   3                                                        27.6*         3.227   2                                                       28.1           3.173   14                                                      21.5           2.839   13                                                       32.2*         2.781   2                                                        32.4*         2.764   2                                                       34.6           2.593   18                                                      40.2           2.244   3                                                       42.5           2.127   4                                                       47.3           1.922   4                                                       51.8           1.765   8                                                       ______________________________________                                          *impurity peak                                                           

(c) The species denominated herein as CoAPSO-20 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XX-A:

                  TABLE XX-A                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         13.9-14.0    6.37-6.33 m                                                       19.7-19.8    4.51-4.48 m                                                       24.2-24.3    3.68-3.66 vs                                                      28.0-28.1    3.187-3.175                                                                              w                                                       31.4-31.5    2.849-2.840                                                                              w                                                       34.5-34.6    2.600-2.592                                                                              w                                                       ______________________________________                                    

(d) The CoAPSO-20 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXI-A:

                  TABLE XXI-A                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         13.9-14.0     6.37-6.33 44-75                                                  19.7-19.8     4.51-4.48 38-42                                                  22.1-22.2     4.02-4.00 3-4                                                    24.2-24.3     3.68-3.66 100                                                    28.0-28.1     3.187-3.175                                                                              11-14                                                  31.4-31.5     2.849-2.840                                                                              11-12                                                  34.5-34.6     2.600-2.592                                                                              16-18                                                  40.1-40.2     2.249-2.243                                                                              3-4                                                    42.5-42.6     2.127-2.122                                                                              3-4                                                    47.3-47.4     1.922-1.918                                                                              4-5                                                    51.8-51.9     1.765-1.762                                                                              8-9                                                    ______________________________________                                    

EXAMPLE 114A

(a) The as-synthesized CoAPSO-31 of example 101A was subjected to analysis by x-ray. The CoAPSO-31 product was characterized by the x-ray powder diffraction pattern of Table XXII-A below:

                  TABLE XXII-A                                                     ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          8.5          10.35   58                                                       17.1          5.19    5                                                        18.4          4.82    2                                                        20.3          4.38    42                                                       21.1          4.20    4                                                        22.1          4.03    28                                                       22.7          3.93    100                                                      23.2          3.83    2                                                        25.2          3.537   4                                                        25.7          3.464   3                                                        28.0          3.187   12                                                       29.8          3.000   6                                                        31.8          2.816   20                                                       35.2          2.549   9                                                        36.2          2.482   2                                                        37.2          2.417   2                                                        37.7          2.386   2                                                        38.3          2.352   2                                                        39.4          2.288   3                                                        39.7          2.271   2                                                        40.3          2.239   2                                                        45.3          2.002   2                                                        46.8          1.943   2                                                        48.7          1.869   2                                                        51.7          1.768   4                                                        ______________________________________                                    

(b) CoAPSO-31 of part (a) was calcined in air at 500° for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXIII-A below:

                  TABLE XXIII-A                                                    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          8.5          10.36   73                                                       14.8          5.99    4                                                        17.1          5.19    10                                                       18.4          4.81    4                                                        20.3          4.37    56                                                       21.4          4.15    3                                                        22.1          4.03    47                                                       22.7          3.93    100                                                      23.4          3.80    3                                                        25.2          3.530   6                                                        25.7          3.464   7                                                        28.0          3.184   15                                                       29.8          2.300   10                                                       31.0          2.885   2                                                        31.8          2.813   31                                                       35.2          2.548   10                                                       36.3          2.476   5                                                        37.3          2.409   3                                                        37.7          2.385   3                                                        38.3          2.348   3                                                        39.4          2.287   4                                                        39.7          2.270   3                                                        40.3          2.237   3                                                        46.7          1.944   5                                                        47.6          1.910   3                                                        48.7          1.868   3                                                        49.3          1.849   2                                                        51.7          1.768   6                                                        ______________________________________                                    

(c) The species denominated herein as CoAPSO-31 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIV-A:

                  TABLE XXIV-A                                                     ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         8.5-8.6     10.40-10.28                                                                              m                                                        20.2-20.3   4.40-4.37 m                                                        22.0-22.1   4.04-4.02 m                                                        22.6-22.7   3.93-3.92 vs                                                       28.0-28.1   3.187-3.175                                                                              w                                                        31.7-31.8   2.823-2.814                                                                              m                                                        ______________________________________                                    

(d) The CoAPSO-31 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXV-A:

                  TABLE XXV-A                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.5-8.6       10.40-10.28                                                                              58-73                                                  14.7-14.8     6.03-5.99 2-4                                                    17.0-17.2     5.22-5.16  5-10                                                  18.4-18.5     4.82-4.80 2-4                                                    20.2-20.3     4.40-4.37 42-56                                                  21.1-21.4     4.21-4.15 3-4                                                    22.0-22.1     4.04-4.02 28-47                                                  22.6-22.7     3.93-3.92 100                                                    23.2-23.4     3.83-3.80 2-3                                                    25.1-25.2     3.548-3.534                                                                              4-6                                                    25.7-25.8     3.466-3.453                                                                              3-7                                                    28.0-28.1     3.187-3.175                                                                              12-15                                                  29.7-29.8     3.008-2.998                                                                               6-10                                                  31.0-31.1     2.885-2.876                                                                              2-4                                                    31.7-31.8     2.823-2.814                                                                              20-31                                                  35.2-35.3     2.550-2.543                                                                               9-10                                                  36.2-36.3     2.481-2.475                                                                              2-5                                                    37.2-37.3     2.417-2.411                                                                              2-3                                                    37.7-37.8     2.386-2.380                                                                              2-3                                                    38.2-38.4     2.356-2.344                                                                              2-3                                                    39.3-39.4     2.292-2.287                                                                              3-4                                                    39.6-39.7     2.276-2.270                                                                              2-3                                                    40.2-40.3     2.243-2.238                                                                              2-3                                                    45.2-45.3     2.006-2.002                                                                              1-2                                                    46.7-46.8     1.945-1.941                                                                              2-5                                                    47.5-47.6     1.914-1.910                                                                              2-3                                                    48.7-48.8     1.870-1.866                                                                              2-3                                                    49.2-49.3     1.852-1.848                                                                              1-2                                                    51.6-51.7     1.771-1.768                                                                              4-6                                                    ______________________________________                                    

EXAMPLE 115A

(a) The as-synthesized CoAPSO-34 of example 90A was subjected to analysis by x-ray. The CoAPSO-34 product was characterized by the x-ray powder diffraction pattern of Table XXVI-A below:

                  TABLE XXVI-A                                                     ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          9.6          9.22    100                                                      12.9          6.84    11                                                       14.2          6.26    10                                                       16.1          5.51    35                                                       18.1          4.92    15                                                       20.7          4.29    62                                                       22.3          3.98    3                                                        23.2          3.84    4                                                        25.3          3.522   17                                                       26.0          3.430   14                                                       27.7          3.217   2                                                        28.5          3.136   3                                                        29.7          3.010   4                                                        30.7          2.914   25                                                       31.3          2.855   16                                                       31.8          2.817   3                                                        34.5          2.597   6                                                        36.3          2.473   3                                                        39.8          2.263   3                                                        43.3          2.090   3                                                        43.6          2.075   3                                                        47.6          1.911   2                                                        47.8          1.904   3                                                        49.2          1.853   5                                                        51.1          1.786   3                                                        53.4          1.716   3                                                        54.7          1.678   2                                                        ______________________________________                                    

(b) CoAPSO-34, of example 90A was calcined in air at 600° for 1 hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXVII-A below:

                  TABLE XXVII-A                                                    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          9.6          9.20    100                                                      10.1          8.77    6                                                        13.0          6.80    14                                                       16.2          5.46    8                                                        17.9          4.97    4                                                        18.0          4.94    3                                                        19.3          4.60    4                                                        20.5          4.34    3                                                        20.8          4.27    14                                                       21.4          4.15    4                                                        23.3          3.82    2                                                        24.3          3.67    3                                                        25.1           3.543  3                                                        25.3           3.524  3                                                        25.7           3.464  2                                                        26.2           3.402  5                                                        31.0           2.831  10                                                       31.6           2.835  5                                                        31.8           2.815  3                                                        ______________________________________                                    

(c) The species denominated herein as CoAPSO-34 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions, being as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXVIII-A:

                  TABLE XXVIII-A                                                   ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         9.4-9.8     9.41-9.03 s-vs                                                     12.86-13.06 6.86-6.76 w                                                        14.08-14.30 6.28-6.19 w-m                                                      15.90-16.20 5.57-5.47 vw-m                                                     20.60-20.83 4.31-4.26 w-vs                                                     30.50-30.80 2.931-2.903                                                                              w-m                                                      ______________________________________                                    

(d) The CoAPSO-34 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXIX-A:

                  TABLE XXIX-A                                                     ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         9.4-9.8        9.41-9.03 87-100                                                10.09-10.14    8.77-8.72 1-6                                                   12.86-13.06    6.86-6.76 11-18                                                 14.08-14.30    6.28-6.19 10-24                                                 15.90-16.24    5.57-5.47 8-35                                                  17.85-18.05    4.97-4.92 3-15                                                  19.13-19.48    4.65-4.55 1-4                                                   20.48-20.56    4.34-4.33 sh-3                                                  20.60-20.83    4.31-4.26 14-100                                                21.41-22.35    4.15-3.98 3-4                                                   23.18-23.31    3.84-3.82 2-3                                                   24.25-24.53    3.67-3.63 0-3                                                   25.13-25.29    3.543-3.520                                                                              3-17                                                  25.72-25.98    3.464-3.430                                                                              3-14                                                  26.06-26.19    3.414-3.402                                                                              5-9                                                   27.73-27.80    3.217-3.209                                                                              2-16                                                  28.30-28.46    3.153-3.136                                                                              3-9                                                   29.50-29.68    3.028-3.010                                                                              4-14                                                  30.50-30.80    2.931-2.903                                                                              12-25                                                 31.04-31.33    2.881-2.855                                                                              7-16                                                  31.60-31.79    2.831-2.815                                                                              3-5                                                   34.40-34.53    2.607-2.597                                                                              5-6                                                   36.20-36.32    2.481-2.473                                                                              3-8                                                   38.40-38.60    2.344-2.332                                                                              3-5                                                   39.70-39.83    2.270-2.263                                                                              3-4                                                   43.10-43.28    2.099-2.090                                                                              sh-6                                                  43.40-43.61    2.045-2.075                                                                              3-10                                                  47.40-47.59    1.918-1.911                                                                              sh-2                                                  47.77- 47.80   1.904-1.903                                                                              3-10                                                  49.17-49.20    1.853-1.852                                                                              5-10                                                  49.90-50.40    1.828-1.809                                                                              0-11                                                  51.13-51.20    1.786-1.784                                                                              3-10                                                  53.20-53.39    1.722-1.716                                                                              3-10                                                  54.60-54.70    1.681-1.678                                                                              2-7                                                   55.80-55.90    1.647-1.645                                                                              2-10                                                  ______________________________________                                    

EXAMPLE 116A

(a) The as-synthesized CoAPSO-35 of example 10A was subjected to analysis by x-ray. The CoAPSO-35 product was characterized by the x-ray powder diffraction pattern of Table XXX-A below:

                  TABLE XXX-a                                                      ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.9*          11.19    8                                                       8.6           10.28   18                                                      10.9           8.12    45                                                      11.6           7.63     8                                                      13.4           6.61    30                                                      15.9           5.57    15                                                      17.3           5.13    83                                                      17.8           4.98    20                                                      20.9           4.25    58                                                      21.9           4.06    100                                                     22.7           3.92    13                                                      23.3           3.82    38                                                      24.9           3.58    13                                                      25.6           3.480    8                                                      26.9           3.314   28                                                      28.3           3.153   45                                                      29.1           3.069   13                                                       31.4*         2.849   10                                                      32.2           2.780   40                                                      34.3           2.614   10                                                       35.2*         2.550    8                                                      35.9           2.501    8                                                      37.8           2.380    5                                                      39.4           2.287    5                                                      41.9           2.156    8                                                      42.6           2.122   10                                                      44.6           2.032    8                                                      47.8           1.903    8                                                      48.6           1.873    8                                                      49.8           1.831   10                                                      51.2           1.784   10                                                      55.7           1.650    8                                                      ______________________________________                                          *impurity peak                                                           

(b) CoAPSO-35, of example 10A was calcined in air at 500° C. for two hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXI-A below:

                  TABLE XXXI-A                                                     ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.7           10.16   26                                                      11.0           8.04    90                                                      11.8           7.50    21                                                      13.7           6.46    100                                                     16.2           5.47    16                                                      17.4           5.10    26                                                      17.6           5.04    37                                                      21.2           4.19    42                                                      22.3           3.99    58                                                      23.2           3.83    26                                                      23.7           3.75    37                                                      25.1           3.548   26                                                      25.3           3.520   32                                                      26.3           3.389   26                                                      27.5           3.243   42                                                      28.6           3.121   53                                                      28.8           3.100   53                                                      29.6           3.018   32                                                       31.9*         2.805   26                                                      32.8           2.730   42                                                      34.5           2.600   21                                                      35.0           2.564   21                                                      35.8           2.508   16                                                      ______________________________________                                          *impurity peak                                                           

(c) The species denominated herein as CoAPSO-35 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXII-A:

                  TABLE XXXII-A                                                    ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         10.9-11.0   8.12-8.04 m-vs                                                     13.4-13.7   6.61-6.46 m-vs                                                     17.3-17.4   5.13-5.10 m-s                                                      20.9-21.2   4.25-4.19 m                                                        21.9-22.3   4.06-3.99 m-s                                                      28.3-28.6   3.153-3.121                                                                              m                                                        ______________________________________                                    

(d) The CoAPSO-35 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXIII-A:

                  TABLE XXXIII-A                                                   ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         7.9*           11.19     8                                                     8.6-8.7        10.28-10.16                                                                              18-26                                                 10.9-11.0      8.12-8.04 45-90                                                 11.6-11.8      7.63-7.50  8-21                                                 13.4-13.7      6.61-6.46  30-100                                               15.9-16.2      5.57-5.47 15-16                                                 17.3-17.4      5.13-5.10 26-83                                                 17.6-17.8      5.04-5.98 20-37                                                 20.9-21.2      4.25-4.19 42-58                                                 21.9-22.3      4.06-3.99  58-100                                               22.7-23.2      3.92-3.83 13-26                                                 23.3-23.7      3.83-3.75 37-38                                                 24.9-25.1       3.58-3.548                                                                              13-26                                                 25.3           3.520     32                                                    25.6-26.3      3.480-3.389                                                                               8-26                                                 26.9-27.5      3.314-3.243                                                                              28-42                                                 28.3-28.6      3.153-3.121                                                                              45-53                                                 28.8-29.6      3.100-3.018                                                                              13-53                                                 31.4-31.9      2.849-2.805                                                                              10-26                                                 32.2-32.8      2.780-2.730                                                                              40-42                                                 34.3-34.5      2.614-2.600                                                                              10-21                                                  35.0-35.2*    2.564-2.550                                                                               8-21                                                 35.8-35.9      2.508-2.501                                                                               8-16                                                 37.8-37.9      2.380-2.374                                                                              5                                                     39.4-39.5      2.287-2.281                                                                              5                                                     41.9-42.0      2.156-2.151                                                                              8                                                     42.6-42.7      2.122-2.118                                                                              10                                                    44.6-44.7      2.032-2.027                                                                              8                                                     47.8-47.9      1.903-1.900                                                                              8                                                     48.6-48.7      1.873-1.870                                                                              8                                                     49.8-49.9      1.831- 1.828                                                                             10                                                    51.2-51.3      1.784-1.781                                                                              10                                                    55.6-55.7      1.653-1.650                                                                              8                                                     ______________________________________                                    

EXAMPLE 117A

(a) The as-synthesized CoAPSO-36 of example 93A was subjected to analysis by x-ray. The CoAPSO-36 product was characterized by the x-ray powder diffraction pattern of Table XXXIV-A below:

                  TABLE XXXIV-A                                                    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          7.3          12.11    7                                                        8.0          11.12   100                                                       8.2          10.74   29                                                        9.2          9.65     4                                                       12.9          6.86     5                                                       13.6          6.52     8                                                       13.7          6.48     8                                                       15.9          5.57    14                                                       16.5          5.38    42                                                       18.4          4.83     6                                                       19.1          4.64    37                                                       20.8          4.27    49                                                       21.6          4.12     7                                                       21.8          4.09    22                                                       22.1          4.03    28                                                       22.6          3.94    29                                                       23.0          3.86     9                                                       24.0          3.71     9                                                       27.3           3.267  20                                                       27.7           3.226   7                                                       28.4           3.148  13                                                       28.7           3.116   5                                                       29.2           3.063  12                                                       30.4           2.940   7                                                       32.1           2.792  12                                                       34.9           2.571  12                                                       ______________________________________                                    

(b) CoAPSO-36, of example 93A was calcined in air at 500° for one hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXV-A below:

                  TABLE XXXV-A                                                     ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          7.4          12.00    8                                                        8.0          11.10   100                                                       8.3          10.69   33                                                       13.6          6.52    13                                                       15.9          5.58     8                                                       16.6          5.36    32                                                       19.3          4.59    29                                                       20.8          4.27    26                                                       21.5          4.14     8                                                       21.8          4.07    11                                                       22.3          3.98    19                                                       22.7          3.92    17                                                       24.0          3.71     7                                                       27.3           3.266  19                                                       27.3           3.215  10                                                       28.8           3.154  12                                                       28.4           3.145  13                                                       28.5           3.131  10                                                       29.2           3.062  13                                                       32.0           2.797  10                                                       ______________________________________                                    

(c) The species denominated herein as CoAPSO-36 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXVI-A:

                  TABLE XXXVI-A                                                    ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         7.8-8.0     11.33-11.05                                                                              vs                                                       8.2-8.3     10.78-10.65                                                                              m                                                        16.4-16.6   5.40-5.34 m                                                        19.0-19.3   4.67-4.60 m                                                        20.7-21.0   4.29-4.23 m                                                        22.3-22.6   3.99-3.93 w-m                                                      ______________________________________                                    

(d) The CoAPSO-36 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXVII-A:

                  TABLE XXXVII-A                                                   ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         7.3-7.5       12.11-11.79                                                                              7-8                                                    7.8-8.0       11.33-11.05                                                                              100                                                    8.2-8.3       10.78-10.65                                                                              29-33                                                  9.2-9.3       9.61-9.51 4-5                                                    12.9-13.0     6.86-6.81 4-5                                                    13.5-13.6     6.56-6.51  8-13                                                  13.7          6.46      7-8                                                    15.8-16.0     5.61-5.54  8-14                                                  16.4-16.6     5.40-5.34 32-42                                                  18.4          4.82      4-6                                                    19.0-19.3     4.67-4.60 29-36                                                  20.7-21.0     4.29-4.23 26-49                                                  21.5-21.7     4.13-4.10 7-8                                                    21.8-22.0     4.08-4.04 11-22                                                  22.3-22.6     3.99-3.93 17-29                                                  22.9-23.0     3.88-3.87 5-9                                                    23.9-24.0     3.72-3.71 7-9                                                    27.2-27.3     3.278-3.267                                                                              19-20                                                  27.6-27.8     3.232-3.209                                                                               7-10                                                  28.3-28.4     3.153-3.143                                                                              12-13                                                  28.5-28.7     3.132-3.110                                                                               5-10                                                  29.0-29.2     3.079-3.058                                                                              12-13                                                  30.3-30.4     2.950-2.940                                                                              5-7                                                    32.0-32.1     2.797-2.788                                                                              10-12                                                  34.7-34.9     2.585-2.571                                                                              10-12                                                  ______________________________________                                    

EXAMPLE 118A

(a) The as-synthesized CoAPSO-39 of example 45A was subjected to analysis by x-ray. The CoAPSO-39 product was characterized by the x-ray powder diffraction pattern of Table XXXVIII-A below:

                  TABLE XXXVIII-A                                                  ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.0*          11.05   31                                                       9.4**         9.41    47                                                       13.1*         6.76    22                                                       13.3          6.66    16                                                       14.8*         5.99    9                                                        15.6*         5.68    31                                                       16.2*         5.47    6                                                        18.1          4.90    16                                                       19.0*         4.67    9                                                        20.2*         4.40    41                                                       21.0**        4.23    100                                                      22.1*         4.02    53                                                       22.4**        3.97    53                                                       22.6*         3.93    69                                                       23.1*         3.85    66                                                       24.7*         3.60    13                                                       26.4**        3.376   28                                                       26.9          3.314   13                                                       27.7*         3.220   13                                                       28.1          3.175   13                                                       28.6**        3.121   25                                                       29.4          3.038   13                                                       30.2          2.959   13                                                       31.4*         2.849   13                                                       32.7**        2.739   22                                                       34.2**        2.622   16                                                       34.6          2.592   6                                                        36.2          2.481   6                                                        37.6          2.392   16                                                       37.8**        2.380   16                                                       39.4**        2.287   9                                                        42.9**        2.108   9                                                        44.6**        2.032   9                                                        48.6          1.873   6                                                        50.6*         1.804   6                                                        51.4          1.778   6                                                        54.5**        1.684   9                                                        55.6**        1.653   6                                                        ______________________________________                                          *peak resulting from CoAPSO11                                                  **peak resulting from CoAPSO11 and CoAPSO 39                             

(b) The species denominated herein as CoAPSO-39 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXIX-A:

                  TABLE XXXIX-A                                                    ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.4-9.5      9.41-9.31 m                                                       13.3-13.4    6.66-6.61 m                                                       18.1-18.2    4.90-4.87 w-m                                                     21.0-21.2    4.23-4.19 vs                                                      22.4-22.5    3.97-3.95 m-s                                                     26.4-26.5    3.376-3.363                                                                              m                                                       ______________________________________                                    

(c) The CoAPSO-39 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXX-A:

                  TABLE XXXX-A                                                     ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.4-9.5       9.41-9.31 31-43                                                  13.3-13.4     6.66-6.61 22-30                                                  18.1-18.2     4.90-4.87 16-31                                                  21.0-21.2     4.23-4.19 100                                                    22.4-22.5     3.97-3.95 53-80                                                  26.4-26.5     3.376-3.363                                                                              28-29                                                  26.9-27.0     3.314-3.302                                                                               6-13                                                  28.1-28.2     3.175-3.164                                                                              13-15                                                  28.6-28.7     3.121-3.11                                                                               10-25                                                  29.4-29.5     3.038-3.028                                                                              13-18                                                  30.2          2.959     13-15                                                  32.7-32.8     2.739-2.730                                                                              17-22                                                  34.2-34.3     2.622-2.614                                                                              12-16                                                  34.5-34.6     2.617-2.592                                                                               6-10                                                  36.2-36.3     2.481-2.475                                                                              6-8                                                    37.6-37.9     2.392-2.374                                                                              16-17                                                  39.4-39.5     2.287-2.281                                                                               9-11                                                  42.9-43.0     2.108-2.103                                                                              8-9                                                    44.6-44.8     2.032-2.023                                                                              6-9                                                    48.5-48.6     1.877-1.873                                                                              5-6                                                    51.4-51.6     1.778-1.771                                                                              5-6                                                    54.5-54.6     1.684-1.681                                                                               9-10                                                  55.4-55.6     1.658-1.653                                                                              5-6                                                    ______________________________________                                    

EXAMPLE 119A

(a) The as-synthesized CoAPSO-44 of example 19A was subjected to analysis by x-ray. The CoAPSO-44 product was characterized by the x-ray powder diffraction pattern of Table XXXXI-A below:

                  TABLE XXXXI-A                                                    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         4.8*          18.41   8                                                        9.4           9.41    100                                                      13.1          6.76    22                                                       13.9          6.37    5                                                        15.9          5.57    (sh)                                                     16.2          5.47    37                                                       17.4          5.10    5                                                        19.0          4.67    9                                                        20.8          4.27    72                                                       21.8          4.08    17                                                       22.7          3.92    9                                                        23.1          3.85    9                                                        24.4          3.65    49                                                       26.2          3.401   31                                                       27.8          3.209   11                                                       29.0          3.079   sh                                                       29.7          3.008   8                                                        30.1          2.969   20                                                       30.8          2.903   49                                                       31.6          2.831   3                                                        32.5          2.755   6                                                        32.9          2.722   6                                                        34.8          2.578   5                                                        35.5          2.529   9                                                        38.6          2.332   5                                                        39.3          2.292   3                                                        39.8          2.265   sh                                                       40.0          2.254   6                                                        42.2          2.141   5                                                        42.6          2.122   5                                                        43.7          2.071   3                                                        44.4          2.040   3                                                        46.2          1.965   3                                                        47.3          1.922   3                                                        48.2          1.888   12                                                       48.7          1.870   8                                                        50.3          1.814   15                                                       52.0          1.759   5                                                        53.8          1.704   9                                                        54.8          1.675   3                                                        ______________________________________                                    

(b) CoAPSO-44 of example 19A was calcined in air at 500° for 1.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXXII-A below:

                  TABLE XXXXII-A                                                   ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.9           9.94    20                                                       9.3           9.51    100                                                      12.9          6.86    24                                                       14.0          6.33    5                                                        15.8          5.61    sh                                                       16.0          5.54    14                                                       17.8          4.98    18                                                       19.1          4.65    4                                                        20.5          4.33    40                                                       22.1          4.02    4                                                        22.3          3.99    4                                                        23.0          3.87    7                                                        25.1          3.548   12                                                       25.8          3.453   13                                                       27.6          3.232   3                                                        28.2          3.164   4                                                        29.5          3.028   3                                                        30.6          2.921   21                                                       31.1          2.876   14                                                       31.7          2.823   4                                                        32.2          2.780   2                                                        33.4          2.683   3                                                        33.7          2.660   4                                                        34.5          2.600   8                                                        36.2          2.481   5                                                        38.2          2.356   2                                                        38.7          2.327   3                                                        39.2          2.298   2                                                        39.8          2.265   3                                                        42.9          2.108   3                                                        43.4          2.085   4                                                        47.6          1.910   3                                                        49.0          1.859   5                                                        49.8          1.831   3                                                        50.6          1.804   3                                                        51.0          1.791   4                                                        53.2          1.722   3                                                        54.7          1.678   2                                                        ______________________________________                                    

(c) The species denominated herein as CoAPSO-44 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXIII-A:

                  TABLE XXXXIII-A                                                  ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.3-9.5      9.51-9.31 vs                                                      16.0-16.3    5.54-5.44 w-m                                                     20.5-20.8    4.33-4.27 m                                                       24.3-25.1     3.66-3.548                                                                              w-m                                                     25.8-26.2    3.453-3.401                                                                              w-m                                                     30.7-31.1    2.912-2.876                                                                              vw-m                                                    ______________________________________                                    

(d) The CoAPSO-44 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXXIV-A:

                  TABLE XXXXIV-A                                                   ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         4.8*          18.41     8                                                      8.9            9.94     20                                                     9.3-9.5       9.51-9.31 100                                                    12.9-13.1     6.86-6.76 22-24                                                  13.7-14.0     6.46-6.33 5-6                                                    15.8-15.9     5.61-5.57 sh                                                     16.0-16.3     5.54-5.44 14-37                                                  17.4-17.8     5.10-4.98  5-18                                                  18.9-19.1     4.70-4.65 4-9                                                    20.5-20.8     4.33-4.27 40-72                                                  21.8-22.1     4.08-4.02  4-17                                                  22.3-22.7     3.99-3.92 4-9                                                    23.0-23.1     3.87-3.85 7-9                                                    24.3-25.1      3.66-3.548                                                                              12-49                                                  25.8-26.2     3.453-3.401                                                                              13-31                                                  27.6-27.8     3.232-3.209                                                                               3-11                                                  28.2          3.164     4                                                      29.0-29.5     3.079-3.028                                                                              sh-3                                                   29.7-30.6     3.008-2.921                                                                               8-21                                                  30.7-31.1     2.912-2.876                                                                               4-49                                                  31.6-31.7     2.831-3.823                                                                              3-4                                                    32.2          2.780     2                                                      32.5-33.7     2.755-2.660                                                                              3-6                                                    34.5-34.8     2.600-2.578                                                                              5-8                                                    35.4-36.2     2.536-2.481                                                                              5-9                                                    38.2-38.6     2.356-2.332                                                                              2-5                                                    38.7-39.3     2.327-2.292                                                                              2-3                                                    39.8-40.0     2.265-2.254                                                                              sh-3                                                   42.2-42.9     2.141-2.108                                                                              3-5                                                    43.4-43.7     2.085-2.071                                                                              3-4                                                    44.4-46.2     2.040-1.965                                                                              3                                                      47.3-47.6     1.922-1.910                                                                              3                                                      48.1-49.0     1.892-1.859                                                                               5-12                                                  49.8-50.3     1.831-1.814                                                                               3-15                                                  50.6          1.804     3                                                      51.0-52.0     1.791-1.759                                                                              4-5                                                    53.2-53.8     1.722-1.704                                                                              3-9                                                    54.7-54.8     1.678-1.675                                                                              2-3                                                    ______________________________________                                    

EXAMPLE 120A

(a) The as-synthesized CoAPSO-46 of example 36 was subjected to analysis by x-ray. The CoAPSO-46 product was characterized by the x-ray powder diffraction pattern of Table XXXXV-A below:

                  TABLE XXXXV-A                                                    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         6.6           13.39   11                                                       6.9           12.81   7                                                        7.2           12.28   12                                                       7.7           11.48   100                                                      12.5          7.08    7                                                        13.1          6.76    5                                                        13.3          6.66    6                                                        13.5          6.56    4                                                        15.0          5.91    4                                                        15.4          5.75    5                                                        16.1          5.51    3                                                        16.8          5.28    6                                                        17.4          5.10    4                                                        17.5          5.07    5                                                        19.9          4.46    5                                                        20.6          4.31    5                                                        21.0          4.23    4                                                        21.4          4.15    sh                                                       21.7          4.10    13                                                       22.2          4.00    3                                                        22.9          3.88    7                                                        23.8          3.74    4                                                        24.3          3.66    5                                                        26.3          3.389   3                                                        26.9          3.314   7                                                        27.8          3.209   10                                                       28.3          3.153   5                                                        28.8          3.010   6                                                        29.9          2.988   4                                                        30.2          2.959   4                                                        30.7          2.912   4                                                        30.9          2.894   4                                                        31.2          2.867   5                                                        31.8          2.814   3                                                        33.0          2.714   4                                                        34.2          2.622   3                                                        36.0          2.495   5                                                        36.6          2.455   3                                                        44.0          2.058   3                                                        ______________________________________                                    

(b) The species denominated herein as CoAPSO-46 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXVI-A:

                  TABLE XXXXVI-A                                                   ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         6.5-6.7      13.60-13.19                                                                              w                                                       7.2-7.4      12.28-11.95                                                                              w                                                       7.6-7.8      11.63-11.33                                                                              vs                                                      21.6-21.7    4.11-4.10 w                                                       27.8-27.9    3.209-3.198                                                                              w                                                       ______________________________________                                    

(c) The CoAPSO-46 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXXVII-A:

                  TABLE XXXXVII-A                                                  ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         6.5-6.7       13.60-13.19                                                                              11                                                     6.9-7.0       12.81-12.63                                                                              7                                                      7.2-7.4       12.28-11.95                                                                              12                                                     7.6-7.8       11.63-11.33                                                                              100                                                    12.5-12.6     7.08-7.03 7                                                      13.1-13.3     6.76-6.66 5                                                      13.5-13.9     6.56-6.37 4                                                      15.0-15.1     5.91-5.87 4                                                      15.4          5.75      5                                                      16.1          5.51      3                                                      16.7-16.8     5.31-5.28 6                                                      17.4-17.5     5.10-5.07 4                                                      19.9-20.0     4.46-4.44 5                                                      20.5-20.6     4.33-4.31 5                                                      21.0          4.23      4                                                      21.4          4.15      sh                                                     21.6-21.7     4.11-4.10 13                                                     22.1-22.2     4.02-4.00 3                                                      22.8-22.9     3.90-3.88 7                                                      23.8          3.74      4                                                      24.2-24.3     3.68-3.66 5                                                      26.3-26.4     3.389-3.376                                                                              3                                                      26.8-26.9     3.326-3.314                                                                              7                                                      27.8-27.9     3.209-3.198                                                                              10                                                     28.3-28.4     3.153-3.143                                                                              5                                                      28.8-28.9     3.010-3.089                                                                              6                                                      29.8-29.9     2.998-2.988                                                                              4                                                      30.2          2.959     4                                                      30.7          2.912     4                                                      30.9-31.0     2.894-2.885                                                                              4                                                      31.2-31.3     2.867-2.858                                                                              5                                                      31.8-31.9     2.814-2.805                                                                              3                                                      32.8-33.0     2.730-2.714                                                                              4                                                      34.2-34.3     2.622-2.614                                                                              3                                                      35.9-36.0     2.510-2.495                                                                              5                                                      36.5-36.6     2.462-2.455                                                                              3                                                      44.0-44.1     2.058-2.053                                                                              3                                                      ______________________________________                                    

EXAMPLE 121A

(a) The as-synthesized CoAPSO-47 of example 104A was subjected to analysis by x-ray. The CoAPSO-47 product was characterized by the x-ray powder diffraction pattern of Table XXXXVIII-A below:

                  TABLE XXXXVIII-A                                                 ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          9.4          9.37    94                                                       12.9          6.88    16                                                       13.8          6.40    9                                                        16.0          5.55    40                                                       17.5          5.06    14                                                       18.9          4.69    6                                                        20.6          4.32    100                                                      21.8          4.08    11                                                       22.4          3.97    4                                                        23.0          3.87    12                                                       24.6          3.62    38                                                       25.9          3.443   22                                                       27.6          3.230   11                                                       29.5          3.030   6                                                        30.6          2.926   42                                                       31.5          2.844   3                                                        33.1          2.707   3                                                        34.5          2.602   9                                                        35.7          2.518   7                                                        38.4          2.345   4                                                        39.6          2.275   4                                                        42.5          2.128   4                                                        47.6          1.910   4                                                        48.5          1.877   11                                                       50.3          1.815   7                                                        52.3          1.749   2                                                        53.2          1.721   5                                                        53.9          1.700   3                                                        54.3          1.690   3                                                        ______________________________________                                    

(b) CoAPSO-47, of example 104A was calcined in air at 500° for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXXIX-A below:

                  TABLE XXXXIX-A                                                   ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                          9.6          9.18    100                                                       3.1          6.77    26                                                       14.2          6.23    3                                                        16.3          5.44    10                                                       18.1          4.90    16                                                       19.4          4.58    3                                                        21.0          4.24    26                                                       22.5          3.96    3                                                        23.5          3.79    3                                                        25.5           3.499  11                                                       26.4           3.381  9                                                        28.7           3.113  4                                                        31.2           2.868  14                                                       31.7           2.824  6                                                        ______________________________________                                    

(c) The species denominated herein as CoAPSO-47 has a three-dimensional microporous crystal framework structure of CoO₂, AlO₂, PO₂ and SiO₂ tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table LI-A:

                  TABLE LI-A                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.4-9.6      9.41-9.21 vs                                                      12.8-13.1    6.92-6.76 w-m                                                     16.0-16.3    5.54-5.44 w-m                                                     20.6-21.0    4.31-4.23 m-vs                                                    25.5-25.9    3.493-3.440                                                                              w-m                                                     30.6-31.1    2.921-2.876                                                                              w-m                                                     ______________________________________                                    

(d) The CoAPSO-47 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table LII-A:

                  TABLE LII-A                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.4-9.6       9.41-9.21  94-100                                                12.8-13.1     6.92-6.76 16-26                                                  13.8-14.2     6.42-6.24 3-9                                                    16.0-16.3     5.54-5.44 10-40                                                  17.5-18.1     5.07-4.90 14-16                                                  18.9-19.4     4.70-4.58 3-6                                                    20.6-21.0     4.31-4.23  26-100                                                21.8          4.08      11                                                     22.4-22.5     3.97-3.95 3-4                                                    23.0-23.5     3.87-3.79  3-12                                                  24.6          3.62      38                                                     25.5-25.9     3.493-3.440                                                                              11-22                                                  26.4          3.376     9                                                      27.6          3.232     11                                                     28.7          3.110     4                                                      29.5          3.028     6                                                      30.6-31.1     2.921-2.876                                                                              13-42                                                  31.5-31.7     2.840-2.823                                                                              3-6                                                    33.1          2.706     3                                                      34.5          2.600     9                                                      35.7          2.515     7                                                      38.4          2.344     4                                                      39.6          2.276     4                                                      42.5          2.127     4                                                      47.6          1.910     4                                                      48.5          1.877     11                                                     50.3          1.814     7                                                      52.3          1.749     2                                                      53.2          1.722     5                                                      53.9          1.701     3                                                      54.3          1.689     3                                                      ______________________________________                                    

EXAMPLE 122A

In order to demonstrate the catalytic activity of the CoAPSO compositions, calcined samples of the CoAPSO products were tested for catalytic cracking by n-butane cracking.

The n-butane cracking was carried out using a bench scale rector. The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoAPSO's which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the CoAPSO had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. In some instances, samples were calcined in situ. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the CoAPSO compositions. The k_(A) value (cm³ /g min) obtained for the CoAPSO compositions are set forth, below.

    ______________________________________                                         CoAPSO                                                                         of Example No:    Rate Constant (k.sub.A)                                      ______________________________________                                         CoAPSO-11 (Ex. 50A)                                                                              1.0                                                          CoAPSO-11 (Ex. 42A)*                                                                             2.0                                                          CoAPSO-11 (Ex. 42A)                                                                              1.9                                                          CoAPSO-11 (Ex. 61A)                                                                              1.4                                                          CoAPSO-31 (Ex. 102A)                                                                             2.1                                                          CoAPSO-34 (Ex. 89A)*                                                                             1.5                                                          CoAPSO-34 (Ex. 89A)                                                                              8.7                                                          CoAPSO-34 (Ex. 90A)                                                                              11.8                                                         CoAPSO-34 (Ex. 83A)                                                                              28.1                                                         CoAPSO-34 (Ex. 77A)*                                                                             11.1                                                         CoAPSO-35 (Ex. 10A)*                                                                             1.0                                                          CoAPSO-44 (Ex. 19A)                                                                              18.1                                                         CoAPSO-46 (Ex. 36A)                                                                              2.4                                                          CoAPSO-47 (Ex. 104A)                                                                             2.3                                                          CoAPSO-44 (Ex. 19A)*                                                                             2.7                                                          CoAPSO-36 (Ex. 93A)*                                                                             1.0                                                          CoAPSO-34 (Ex. 83A)*                                                                             4.1                                                          CoAPSO-34 (Ex. 69A)*                                                                             9.4                                                          CoAPSO-34 (Ex. 79A)*                                                                             5.2                                                          CoAPSO-34 (Ex. 78A)*                                                                             4.6                                                          CoAPSO-34 (Ex. 81A)*                                                                             3.3                                                          ______________________________________                                          *calcined in situ at 500° C. in helium for 2 hours prior to             activation.                                                              

MAGNESIUM-ALUMINUM-PHOSPHORUS-SILICON OXIDE MOLECULAR SIEVES

Molecular sieves containing magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents

In the following examples the MgAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isoproproxide;

(b) CATAPAL: Trademark of Condea for hydrated pseudo-boehmite;

(c) LUDOX LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) Mg(Ac)₂ : magnesium acetate tetrahydrate, Mg(C₂ H₃ O₂).4H₂ O;

(e) H₃ PO₄ : 85 weight percent phosporic acid in water;

(f) TBAOH: tetrabutylammonium hydroxide (40 wt. % in water);

(g) Pr₂ NH: di-n-propylamine;

(h) Pr₃ N: tri-n-propylamine;

(i) Quin: Quinuclidine;

(j) MQuin: Methyl Quinuclidine hydroxide (17.9% in water);

(k) C-hex; cyclohexylamine;

(l) TEAOH: tetraethylammonium hydroxide (40 wt. % in water).

(m) DEEA: diethylethanolamine;

(n) i-Pr₂ NH: di-isopropylamine;

(o) TEABr: tetraethylammonium bromide; and

(p) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water).

Preparative Procedure

The MgAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:

    eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide), SiO₂, Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅) and H₂ O, respectively. The values for e, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples.

The reaction mixtures were prepared by three procedures, designated hereinafter as Methods A, B and C, unless otherwise noted in the preparative examples.

Method A was employed for examples 1B to 25B, 27B-30B, 39B-46B, 55B-57B, 61B, 63B-71B, 77B-85B and 87B-106B. Method B was employed for examples 31B-38B and 47B-54B. Method C was employed for examples 26B, 62B and 72-76B. The aluminum source was aluminum iso-propoxide except that CATAPAL was the aluminum source in examples 39B-55B and 58B-61B.

METHOD A

The reaction mixture was prepared by mixing the ground aluminum source (Al-ipro or CATAPAL) with the H₃ PO₄ and water on a gradual basis with occasional cooling with an ice bath. The resulting mixture was blended until a homogeneous mixture was observed. When the aluminum source was CATAPAL the water and H₃ PO₄ were first mixed and the CATAPAL added thereto. The magnesium acetate was dissolved in portion of the water and was then added followed by addition of the LUDOX-LS. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for an effective time. Alternatively, if the digestion temperature was 100° C. the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

METHOD B

When method B was employed the organic templating agent was di-n-propylamine. The aluminum source, silicon source and one-half of the water were first mixed and blended until a homogeneous mixture was observed. A second solution was prepared by mixing the remaining water, the H₃ PO₄ and the magnesium acetate. This solution was then added to the above mixture. The magnesium acetate and H₃ PO₄ solution was then added to the above mixture and blended until a homogeneous mixture was observed. The organic templating agent(s) was then added and the resulting reaction mixture digested and product recovered as was done in Method A.

METHOD C

Method C was carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS. H₃ PO₄ and magnesium acetate were then added to this mixture. The organic templating agent was then added to the resulting mixture and digested and product recovered as was done in Method A.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof.

EXAMPLES 1B TO 90B AND AB TO QB

MgAPSO molecular sieves were prepared according to the above described Methods A, B and C by preparing reaction mixtures expressed as

    eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein, e, f, h, i, g and j represent the moles of template R, magnesium (expressed as the oxide), Al₂ O₃, SiO₂, P₂ O₅ (H₃ PO₃ expressed as P₂ O₅), and H₂ O respectively. The values for e, f, g, h and i for examples 1B to 90B are set forth in Table I-B to VI-B. The value of "j" was 50 in examples 1B to 84B and 87B-90B and was 75B in example 85B and was 71B in example 86B. Tables IB to VI-B also shows the temperature (°C.) and time (hours) employed for digestion and indicates the final MgAPSO(s) formed.

Examples AA to QB represent reaction mixtures wherein crystalline MgAPSO products were not observed when the reaction products were subjected to X-ray analysis. The results of Examples AB to QB are set forth in Table VII-B.

                                      TABLE I-B                                    __________________________________________________________________________                                     MgAPSO                                         Example                                                                             Template                                                                            e f h i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.2                               __________________________________________________________________________      1B  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   48    MgAPSO-5; MgAPSO-36                             2B  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   166   MgAPSO-5; MgAPSO-36                             3B  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   48    MgAPSO-5; MgAPSO-36                             4B  Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   166   MgAPSO-5; MgAPSO-36                             5B.sup.1,3                                                                         Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   88    MgAPSO-36; MgAPSO-5                             6B.sup.1,3                                                                         Pr.sub.3 N                                                                          1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   88    MgAPSO-36; MgAPSO-5                             7B.sup.3                                                                           Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   48    MgAPSO-5; MgAPSO-36                             8B.sup.3                                                                           Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   160   MgAPSO-5; MgAPSO-36                             9B.sup.3                                                                           Pr.sub.3 N                                                                          1.5                                                                              0.9                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   48    MgAPSO-5; MgAPSO-36                            10B.sup.3                                                                           Pr.sub.3 N                                                                          1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   160   MgAPSO-5; MgAPSO-36                            11B.sup.3                                                                           TPAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   48    MgAPSO-5;                                      12B.sup.3                                                                           TPAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   112   MgAPSO-5;                                      13B.sup.3                                                                           TPAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   48    MgAPSO-5; MgAPSO-36                            14B.sup.3                                                                           TPAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   112   MgAPSO-5; MgAPSO-36                            __________________________________________________________________________      .sup.1 Seed crystal of MAPO36 employed, as disclosed in copending U.S.         Ser. No. 514,334.                                                              .sup.2 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.3 LUDOX-LS was added before the magnesium acetate in these example. 

                                      TABLE II-B                                   __________________________________________________________________________                                      MgAPSO                                        Example                                                                             Template                                                                            e f h  i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.1                              __________________________________________________________________________     .sup. 15B.sup.2                                                                     DEEA 1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.6                                                                              150   88    MgAPSO-5; MgAPSO-47                           .sup. 16B.sup.2                                                                     DEEA 1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.6                                                                              200   88    MgAPSO-5; MgAPSO-47                           17B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              150   48    MgAPSO-11; MgAPSO-5;                          18B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              150   166   MgAPSO-11; MgAPSO-5;                                                           MgAPSO-39; MgAPSO-46                          19B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              200   48    MgAPSO-5; MgAPSO-11; MgAPSO-39                20B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              200   166   MgAPSO-11; MgAPSO-39; MgAPSO-5                21B  Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              125   300   MgAPSO-11                                     22B  Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              150   47    MgAPSO-39; MgAPSO-11; MgAPSO-46;                                               MgAPSO-31                                     23B  Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              150   165   MgAPSO-39; MgAPSO-46; MgAPSO-11;                                               MgAPSO-31                                     24B  Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              200   47    MgAPSO-11; MgAPSO-5; MgAPSO-39;                                                MgAPSO-31                                     25B  Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              200   165   MgAPSO-11; MgAPSO-5; MgAPSO-46                26B  Pr.sub.2 NH                                                                         1.0                                                                              0.4                                                                              1.0                                                                               1.0                                                                              0.4                                                                              150   182   MgAPSO-46                                     .sup. 27B.sup.2                                                                     Pr.sub.2 NH                                                                         2.0                                                                              0.9                                                                              0.9                                                                               0.2                                                                              0.2                                                                              150   96    MgAPSO-46                                     .sup. 28B.sup.2                                                                     Pr.sub.2 NH                                                                         2.0                                                                              0.9                                                                              0.9                                                                               0.2                                                                              0.2                                                                              150   238   MgAPSO-46; MgAPSO-11                          .sup. 29B.sup.2                                                                     Pr.sub.2 NH                                                                         2.0                                                                              0.9                                                                              0.9                                                                               0.2                                                                              0.2                                                                              200   96    MgAPSO-11; MgAPSO-46; MgAPSO-39               __________________________________________________________________________      .sup.1 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.2 LUDOX-LS was added before magnesium acetate in these examples.    

                                      TABLE III-B                                  __________________________________________________________________________                                     MgAPSO                                         Example                                                                             Template                                                                            e f h i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.1                               __________________________________________________________________________     30B.sup.2                                                                           Pr.sub.2 NH                                                                         2.0                                                                              0.9                                                                              0.9                                                                              0.2                                                                              0.2                                                                              200   238   MgAPSO-11; MgAPSO-46; MgAPSO-39;                                               MgAPSO-33                                      31B.sup.                                                                            Pr.sub.2 NH                                                                         1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   144   MgAPSO-39; MgAPSO-11; MgAPSO-46                32B.sup.                                                                            Pr.sub.2 NH                                                                         1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   144   MgAPSO-39; MgAPSO-11; MgAPSO-46                33B.sup.                                                                            Pr.sub.2 NH                                                                         1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   144   MgAPSO-39; MgAPSO-11; MgAPSO-46                34B.sup.                                                                            Pr.sub.2 NH                                                                         1.5                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   144   MgAPSO-39; MgAPSO-11; MgAPSO-46                35B.sup.                                                                            Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              2.7                                                                              0.9                                                                              0.2                                                                              150   142   MgAPSO-39; MgAPSO-11                           36B.sup.                                                                            Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              2.7                                                                              0.9                                                                              0.2                                                                              200   142   MgAPSO-11; MgAPSO-39; MgAPSO-46                37B.sup.                                                                            Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              2.7                                                                              0.9                                                                              0.2                                                                              150   142   MgAPSO-46                                      38B.sup.                                                                            Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              2.7                                                                              0.9                                                                              0.2                                                                              200   142   MgAPSO-46                                      39B.sup.2                                                                           Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    96   MgAPSO-11; MgAPSO-39; MgAPSO-46                40B.sup.2                                                                           Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   190   MgAPSO-11; MgAPSO-39; MgAPSO-46                41B.sup.2                                                                           Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200    96   MgAPSO-11; MgAPSO-39; MgAPSO-46                42B.sup.2                                                                           Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   190   MgAPSO-11; MgAPSO-39; MgAPSO-46                43B.sup.2                                                                           Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    96   MgAPSO-46; MgAPSO-20                           44B.sup.2                                                                           Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   190   MgAPSO-46                                      45B.sup.2                                                                           Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200    96   MgAPSO-39; MgAPSO-46                           46B.sup.2                                                                           Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   190   MgAPSO-39; MgAPSO-46                           __________________________________________________________________________      .sup.1 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.2 LUDOX-LS was added before the magnesium acetate in this example.  

                                      TABLE IV-B                                   __________________________________________________________________________                                        MgAPSO                                      Example                                                                             Template                                                                            e f  h  i  g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.4                            __________________________________________________________________________     47B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   94    MgAPSO-11; MgAPSO-39; MgAPSO-5              48B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   238   MgAPSO-11; MgAPSO-39; MgAPSO-5              49B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   94    MgAPSO-11; MgAPSO-39; MgAPSO-5              50B  Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   238   MgAPSO-11; MgAPSO-5; MgAPSO-39;                                                MgAPSO-46                                   51B  Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   94    MgAPSO-46; MgAPSO-39; MgAPSO-5              52B  Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   238   MgAPSO-46; MgAPSO-11; MgAPSO-39             53B  Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   94    MgAPSO-46                                   54B  Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   238   MgAPSO-46; MgAPSO-39                        55B.sup.1,2                                                                         Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150,200                                                                              113   MgAPSO-39; MgAPSO-31; MgAPSO-11             56B  i-Pr.sub.2 NH                                                                       1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   88    MgAPSO-5; MgAPSO-11; MgAPSO-34              57B  i-Pr.sub.2 NH                                                                       1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   88    MgAPSO-5; MgAPSO-11; MgAPSO-34              58B.sup.3,5                                                                         i-Pr.sub.2 NH                                                                       1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              150   96    MgAPSO-5; MgAPSO-11; MgAPSO-39              59B.sup.3,5                                                                         i-Pr.sub.2 NH                                                                       1.0                                                                              0.2                                                                               0.9                                                                               0.9                                                                               0.2                                                                              200   96    MgAPSO-5; MgAPSO-11; MgAPSO-39              60B.sup.5                                                                           i-Pr.sub.2 NH                                                                       1.0                                                                               0.17                                                                              0.92                                                                              0.95                                                                             0.1                                                                              150   93    MgAPSO-5; MgAPSO-11                         61B.sup.5                                                                           i-Pr.sub.2 NH                                                                       1.0                                                                               0.17                                                                              0.92                                                                              0.95                                                                             0.1                                                                              200   93    MgAPSO-5; MgAPSO-39; MgAPSO-11              62B  i-Pr.sub.2 NH                                                                       1.0                                                                              0.4                                                                               1.0                                                                               1.0                                                                               0.4                                                                              150   231   MgAPSO-5; MgAPSO-11                         __________________________________________________________________________      .sup.1 AlPO.sub.4 -31 seed crystal                                             .sup.2 Two mixtures were digested with one at 150° C. and one at        200° C.                                                                 .sup.3 SAPO-11 seed crystal as disclosed in U.S. Ser. No. 400,438              .sup.4 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.5 LUDOX-LS was added before magnesium acetate in this example.      

                                      TABLE V-B                                    __________________________________________________________________________                                     MgAPSO                                         Example                                                                             Template                                                                            e f h i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.1                               __________________________________________________________________________     63B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    48   MgAPSO-34                                      64B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   166   MgAPSO-34                                      65B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200    48   MgAPSO-34; MgAPSO-5                            66B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   166   MgAPSO-34                                      67B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150    40   MgAPSO-34; MgAPSO-5                            68B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   121   MgAPSO-34                                      69B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200    40   MgAPSO-5; MgAPSO-34                            70B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   121   MgAPSO-5; MgAPSO-34                            71B  TEAOH                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   114   MgAPSO-34; MgAPSO-5                            72B  TEAOH                                                                               1.0                                                                              0.4                                                                              1.0                                                                              1.0                                                                              0.4                                                                              100   111   MgAPSO-34                                      73B  TEAOH                                                                               1.0                                                                              0.4                                                                              1.0                                                                              1.0                                                                              0.4                                                                              100   182   MgAPSO-34                                      74B  TEAOH                                                                               1.0                                                                              0.4                                                                              1.0                                                                              1.0                                                                              0.4                                                                              150   111   MgAPSO-34                                      75B  TEAOH                                                                               1.0                                                                              0.4                                                                              1.0                                                                              1.0                                                                              0.4                                                                              150   182   MgAPSO-34                                      76B  TEAOH                                                                               1.0                                                                              0.4                                                                              1.0                                                                              1.0                                                                              0.4                                                                              150   231   MgAPSO-34; MgAPSO-5                            __________________________________________________________________________      .sup.1 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.        

                                      TABLE VI-B                                   __________________________________________________________________________                                     MgAPSO                                         Example                                                                             Template                                                                            e f h i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.1                               __________________________________________________________________________     77B  Quin 1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    48   MgAPSO-35; MgAPSO-16                           78B  Quin 1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   166   MgAPSO-35; MgAPSO-16                           79B  Quin 1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200    48   MgAPSO-35; MgAPSO-16                           80B  Quin 1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   166   MgAPSO-35; MgAPSO-16                           81B  MQuin                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    40   MgAPSO-35                                      82B  MQuin                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150   121   MgAPSO-35                                      83B  MQuin                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200    40   MgAPSO-35                                      84B  MQuin                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              200   121   MgAPSO-35                                      85B  MQuin                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150   114   MgAPSO-35; MgAPSO-16                           .sup. 86B.sup.2                                                                     TBAOH                                                                               2.0                                                                              0.4                                                                              0.8                                                                              1.0                                                                              0.4                                                                              200    48   MgAPSO-5                                       .sup. 87B.sup.3                                                                     C-hex                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150    40   MgAPSO-44; MgAPSO-5                            .sup. 88B.sup.3                                                                     C-hex                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   107   MgAPSO-44; MgAPSO-5                            .sup. 89B.sup.3                                                                     C-hex                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              150    40   MgAPSO-5; MgAPSO-44                            .sup. 90B.sup.3                                                                     C-hex                                                                               1.0                                                                              0.2                                                                              0.9                                                                              0.9                                                                              0.6                                                                              200   107   MgAPSO-5; MgAPSO-44                            __________________________________________________________________________      .sup.1 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.2 The mixing order in this example was in the order of the aluminum       source, magnesium source, silicon source and the phosphorus source.            .sup.3 LUDOX-LS was added before magnesium acetate in this example.      

                                      TABLE VII-B.sup.1                            __________________________________________________________________________     Example                                                                             Template                                                                            e f h  i g j     Temp(°C.)                                                                     Time(hrs)                                                                            Method                                  __________________________________________________________________________     AB   TPABr                                                                               1.0                                                                              0.4                                                                              1.0                                                                               1.0                                                                              0.4                                                                              50    150   231   C                                       BB   Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              50    125    47   A                                       CB   Pr.sub.2 NH                                                                         1.0                                                                              0.1                                                                               0.95                                                                             0.8                                                                              0.4                                                                              50    125   165   A                                       DB   Pr.sub.2 NH                                                                         1.0                                                                              0.4                                                                              1.0                                                                               1.0                                                                              0.4                                                                              50    100   111   C                                       EB   Pr.sub.2 NH                                                                         1.0                                                                              0.4                                                                              1.0                                                                               1.0                                                                              0.4                                                                              50    100   182   C                                       FB   Pr.sub.2 NH                                                                         1.0                                                                              0.4                                                                              1.0                                                                               1.0                                                                              0.4                                                                              50    150   111   C                                       GB   Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    150    96   B                                       HB   Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    150   235   B                                       IB   Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    200    96   B                                       JB   Pr.sub.2 NH                                                                         1.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    200   235   B                                       KB   Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    150    96   B                                       LB   Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    150   235   B                                       MB   Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    200    96   B                                       NB   Pr.sub.2 NH                                                                         2.0                                                                              0.2                                                                              0.9                                                                               0.9                                                                              0.2                                                                              50    200   235   B                                       OB   TBAOH                                                                               2.0                                                                              0.4                                                                              0.8                                                                               1.0                                                                              0.4                                                                              71    150    48   (2)                                     PB   TBAOH                                                                               2.0                                                                              0.4                                                                              0.8                                                                               1.0                                                                              0.4                                                                              71    150   160   (2)                                     QB   TBAOH                                                                               2.0                                                                              0.4                                                                              0.8                                                                               1.0                                                                              0.4                                                                              71    200   160   (2)                                     __________________________________________________________________________      .sup.1 Reaction mixtures from which crystalline MgAPSO products were not       identified by Xray analysis of the products.                                   .sup.2 The mixing order in this example was in the order of the aluminum       source, the magnesium source, the silicon source and the phosphorus            source.                                                                  

EXAMPLES 91B TO 106B

MgAPSO molecular sieves were prepared according to the procedures employed in examples 1B to 90B. The aluminum source was CATAPAL in examples 96B and 97B.

The results of preparative examples 91B to 106B are set forth in Table VIII-B.

                                      TABLE VIII-B                                 __________________________________________________________________________                                      MgAPSO                                        Example.sup.2                                                                       Template                                                                            e f  h i g Temp(°C.)                                                                     Time(hrs)                                                                            Product(s).sup.1                              __________________________________________________________________________      91B MQuin                                                                               1.0                                                                              0.1                                                                               0.9                                                                              0.9                                                                              0.6                                                                              150   450   MgAPSO-35                                      92B TEAOH                                                                               1.0                                                                              0.1                                                                               0.9                                                                              0.9                                                                              0.6                                                                              150    44   MgAPSO-5; MgAPSO-34                            93B TEAOH                                                                               1.0                                                                              0.1                                                                               0.9                                                                              0.9                                                                              0.6                                                                              150    44   MgAPSO-5; MgAPSO-34                            94B TEAOH                                                                               1.0                                                                               0.05                                                                             1.0                                                                              1.0                                                                              0.4                                                                              100   280   MgAPSO-34                                      95B TEAOH                                                                               1.0                                                                              0.1                                                                               1.0                                                                              1.0                                                                              0.4                                                                              100   280   MgAPSO-34                                      96B Pr.sub.2 NH                                                                         2.0                                                                              0.1                                                                               0.9                                                                              0.9                                                                              0.6                                                                              150   122   MgAPSO-43; MgAPSO-46                           97B Pr.sub.2 NH                                                                         2.0                                                                              0.1                                                                               0.9                                                                              0.9                                                                              0.6                                                                              150   122   MgAPSO-43; MgAPSO-46                           98B Quin 1.0                                                                              0.2                                                                               0.9                                                                              0.9                                                                              0.6                                                                              220   114   MgAPSO-16; MgAPSO-35                           99B C-hex                                                                               1.0                                                                              0.2                                                                               0.9                                                                              0.9                                                                              0.6                                                                              220   114   MgAPSO-44; MgAPSO-5                           100B TMAOH                                                                               1.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              100    18   MgAPSO-20                                     101B TMAOH                                                                               1.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              150   111   MgAPSO-20                                     102B TMAOH                                                                               1.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              200    22   MgAPSO-20                                     103B TMAOH                                                                               1.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              200   111   MgAPSO-20                                     104B DEEA 2.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              100   111   MgAPSO-47                                     105B DEEA 2.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              100    22   MgAPSO-47; MgAPSO-5                           106B DEEA 2.0                                                                              0.2                                                                               0.9                                                                              0.7                                                                              0.6                                                                              100   111   MgAPSO-47                                     __________________________________________________________________________      .sup.1 Major species as identified by xray diffraction pattern of product      except that when two or more species were identified the species are           listed in the order of their predominance in the MgAPSO products.              .sup.2 LUDOX-LS was added before magnesium acetate in examples 91B to          106B.                                                                    

EXAMPLE 107B

Samples of the MgAPSO products were subjected to chemical analysis. The chemical analysis for each of the analyzed products is given hereinafter:

(a) The chemical analysis for the MgAPSO-5 of example 4B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.3                                                             P.sub.2 O.sub.5                                                                              45.4                                                             MgO           2.8                                                              SiO.sub.2     3.9                                                              Carbon        5.0                                                              LOI*          13.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anydrous basis) of: 0.23 MgO:1.00 Al₂ O₃ :1.04 P₂ O₅ :0.21 SiO₂ ; and a formula (anhydrous basis) of:

    0.03R(Mg.sub.0.05 Al.sub.0.44 P.sub.0.46 Si.sub.0.05)O.sub.2

(b) The chemical analysis for MgAPSO-36 of example 5B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.2                                                             P.sub.2 O.sub.5                                                                              44.6                                                             MgO           2.6                                                              SiO.sub.2     8.6                                                              Carbon        6.2                                                              LOI*          13.9                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.21 MgO:1.00 Al₂ O₃ :1.03 P₂ O₅ :0.45 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R(Mg.sub.0.05 Al.sub.0.43 P.sub.0.44 Si.sub.0.10)O.sub.2

(c) The chemical analysis for the MgAPSO-46 of example 44B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             30.1                                                             P.sub.2 O.sub.5                                                                              38.4                                                             MgO           4.1                                                              SiO.sub.2     4.4                                                              Carbon        10.6                                                             LOI*          22.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.34 MgO:1.00 Al₂ O₃ :0.92 P₂ O₅ :0.25 SiO₂ : and a formula (anhydrous basis) of:

    0.11R(Mg.sub.0.08 Al.sub.0.45 P.sub.0.41 Si.sub.0.06)O.sub.2

(d) The chemical analysis of the MgAPSO-34 of example 63B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.7                                                             P.sub.2 O.sub.5                                                                              37.0                                                             MgO           3.0                                                              SiO.sub.2     2.9                                                              Carbon        8.3                                                              LOI*          21.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.24 MgO:1.00 Al₂ O₃ :0.84 P₂ O₅ :0.16 SiO₂ ; and a formula (anhydrous basis) of:

    0.07R(Mg.sub.0.06 Al.sub.0.49 P.sub.0.41 Si.sub.0.04)O.sub.2

(e) The chemical analysis for the MgAPSO-34 of example 68B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             29.8                                                             P.sub.2 O.sub.5                                                                              40.4                                                             MgO           2.3                                                              SiO.sub.2     6.9                                                              Carbon        10.4                                                             LOI*          21.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.20 MgO:1.00 Al₂ O₃ :0.97 P₂ O₅ :0.39 SiO₂ : and a formula (anhydrous basis) of:

    0.08R(Mg.sub.0.04 Al.sub.0.44 P.sub.0.43 Si.sub.0.09)O.sub.2

(f) The chemical analysis of the MgAPSO-34 of example 74B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             28.6                                                             P.sub.2 O.sub.5                                                                              33.9                                                             MgO           4.9                                                              SiO.sub.2     3.7                                                              Carbon        9.0                                                              LOI*          27.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.43 MgO;1.00 Al₂ O₃ :0.85 P₂ O₅ :0.22 SiO₂ ; and a formula (anhydrous basis) of:

    0.08R(Mg.sub.0.10 Al.sub.0.46 P.sub.0.38 Si.sub.0.05)O.sub.2

(g) The chemical analysis for the MgAPSO-35 of example 85B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             28.3                                                             P.sub.2 O.sub.5                                                                              42.7                                                             MgO           2.8                                                              SiO.sub.2     4.0                                                              Carbon        9.8                                                              LOI*          19.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.37 R:0.25 MgO:1.0 Al₂ O₃ :1.08 P₂ O₅ :0.24 SiO₂ ; and a formula (anhydrous basis) of:

    0.08(Mg.sub.0.05 Al.sub.0.43 P.sub.0.47 Si.sub.0.05)O.sub.2

(h) The chemical analysis for the MgAPSO-20 of example 101B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.8                                                             P.sub.2 O.sub.5                                                                              31.4                                                             MgO           3.1                                                              SiO.sub.2     15.2                                                             Carbon        9.7                                                              LOI*          21.2                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.74 R:0.28 MgO:1.00 Al₂ O₃ :0.81 P₂ O₅ :0.93 SiO₂ ; and a formula (anhydrous basis) of:

    0.15R(Mg.sub.0.06 Al.sub.0.41 P.sub.0.34 Si.sub.0.19)O.sub.2

(i) The chemical analysis for the MgAPSO-43 of example 97B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.3                                                             P.sub.2 O.sub.5                                                                              33.1                                                             MgO           3.6                                                              SiO.sub.2     8.2                                                              Carbon        9.1                                                              LOI*          21.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.40R:0.28 MgO:1.00 Al₂ O₃ :0.74 P₂ O₅ :0.43 SiO₂ ; and a formula (anhydrous basis) of:

    0.10R(Mg.sub.0.07 Al.sub.0.48 P.sub.0.35 Si.sub.0.10)O.sub.2

(j) The chemical analysis for the MgAPSO-47 of example 104B was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             33.1                                                             P.sub.2 O.sub.5                                                                              29.3                                                             MgO           2.8                                                              SiO.sub.2     7.7                                                              Carbon        5.7                                                              LOI*          25.4                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.24R:0.21 MgO; 1.00 Al₂ O₃ : 0.64 P₂ O₅ : 0.39 SiO₂ ; and a formula (anhydrous basis) of:

    0.06R(Mg.sub.0.06 Al.sub.0.51 P.sub.0.33 Si.sub.0.10)O.sub.2

EXAMPLE 108B

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of examples. Analysis of crystals having a morphology characteristic of the MgAPSO products as prepared in the following referenced examples gave the following analysis based on relative peak heights:

    ______________________________________                                         (a) MgAPSO-5 (Example 4B):                                                               Average of Spot Probes                                               ______________________________________                                         Mg        3                                                                    Al        46                                                                   P         48                                                                   Si        3                                                                    ______________________________________                                         (b) MgAPSO-36 (Example 5B):                                                              Average of Spot Probes                                               ______________________________________                                         Mg        3                                                                    Al        40                                                                   P         48                                                                   Si        9                                                                    ______________________________________                                         (c) MgAPSO-46 (Example 44B):                                                             Average of Spot Probes                                               ______________________________________                                         Mg        5                                                                    Al        39                                                                   P         49                                                                   Si        6                                                                    ______________________________________                                         (d) MgAPSO-34 (Example 63B):                                                             Average of Spot Probes                                               ______________________________________                                         Mg        6                                                                    Al        44                                                                   P         45                                                                   Si        6                                                                    ______________________________________                                         (e) MgAPSO-34 (Example 75B):                                                             Average of Spot Probes                                               ______________________________________                                         Mg        6                                                                    Al        42                                                                   P         44                                                                   Si        8                                                                    ______________________________________                                         (f) MgAPSO-35 (Example 80B):                                                             Average of Spot Probes                                               ______________________________________                                         Mg        4                                                                    Al        41                                                                   P         51                                                                   Si        4                                                                    ______________________________________                                         (g) MgAPSO-47 (Example 104B):                                                            Average of Spot Probes                                               ______________________________________                                         Mg        2                                                                    Al        42                                                                   P         43                                                                   Si        13                                                                   ______________________________________                                    

EXAMPLE 109B

Samples of the MgAPSO products were evaluated for adsorption capacities in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each as-synthesized or calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the selected MgAPSO products were:

    ______________________________________                                         (a) Example 4B (MgAPSO-5):                                                               Kinetic    Pressure Temp  Wt. %                                      Adsorbate Diameter, Å                                                                           (Torr)   (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2   3.46       99       -183  13.2                                       O.sub.2   3.46       749      -183  15.5                                       Cyclohexane                                                                              6.0        57       23.4   7.9                                       neopentane                                                                               6.2        100      23.4   5.0                                       H.sub.2 O 2.65       4.6      23.2  16.0                                       H.sub.2 O 2.65       16.8     23.5  21.3                                       ______________________________________                                          *calcined in air at 600° C. for 2.25 hrs.                         

The above data demonstrate that the pore size of the calcined product is greater than about 6.2 Å.

    ______________________________________                                         (b) Example 101B (MgAPSO-20):                                                            Kinetic    Pressure Temp  Wt. %                                      Adsorbate Diameter, Å                                                                           (Torr)   (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2   3.46       99       -183   0.8                                       O.sub.2   3.46       750      -183   2.7                                       H.sub.2 O 2.65       4.6      23.2  16.5                                       H.sub.2 O 2.65       16.8     23.5  19.9                                       ______________________________________                                          *calcined in air at 600° C. for 1.5 hrs.                          

The above data demonstrate that the pore size of the calcined product is about 3.0 Å.

    ______________________________________                                         (c) Example 63B (MgAPSO-34):                                                             Kinetic    Pressure Temp  Wt. %                                      Adsorbate Diameter, Å                                                                           (Torr)   (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2   3.46       100      -183  21.7                                       O.sub.2   3.46       734      -183  33.6                                       isobutane 5.0        300      23     1.3                                       n-hexane  4.3        51       24    10.4                                       H.sub.2 O 2.65       4.6      23    27.1                                       H.sub.2 O 2.65       18.5     24    32.9                                       ______________________________________                                          *calcined in air at 600° C. for 1.5 hours.                        

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

    ______________________________________                                         (d) Example 84B (MgAPSO-35):                                                             Kinetic    Pressure Temp  Wt. %                                      Adsorbate Diameter, Å                                                                           (Torr)   (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2   3.46       100      -183  6.7                                        O.sub.2   3.46       734      -183  9.2                                        isobutane 5.0        100      24    0.3                                        n-hexane  4.3        51       24    1.1                                        H.sub.2 O 2.65       4.6      23    11.5                                       H.sub.2 O 2.65       19.5     23    17.7                                       ______________________________________                                          *calcined in nitrogen at 500° C. for 2 hrs.                       

    (e) Example 91B (MgAPSO-35):                                                             Kinetic    Pressure Temp  Wt. %                                      Adsorbate Diameter, Å                                                                           (Torr)   (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2   3.46       100      -183  11.2                                       O.sub.2   3.46       744      -183  14.0                                       isobutane 5.0        100      22.8   0.2                                       n-hexane  4.3         49      22.3   5.7                                       H.sub.2 O 2.65        4.6     23.1  16.1                                       H.sub.2 O 2.65       17.8     22.9  20.5                                       ______________________________________                                          *calcined at 500° in air for 6.7 hours.                           

The above data demonstrate that the pore size of the calcined product is about 4.3 Å. In addition, the data demonstrate that in part (d) the template was not sufficiently removed by the calcination.

    ______________________________________                                         (f) Example 5B (MgAPSO-36):                                                             Kinetic   Pressure  Temp  Wt. %                                       Adsorbate                                                                               Diameter, Å                                                                          (Torr)    (°C.)                                                                         Adsorbed*                                   ______________________________________                                         O.sub.2  3.46      100       -183  12.9                                        O.sub.2  3.46      734       -183  15.4                                        isobutene                                                                               5.0       100       24    5.2                                         cyclohexane                                                                             6.0       59        23.7  9.0                                         neopentane                                                                              6.2       100       24.5  5.5                                         H.sub.2 O                                                                               2.65      4.6       23    16.8                                        H.sub.2 O                                                                               2.65      20        23.6  23.5                                        ______________________________________                                          *calcined in air at 500° C. for 2.0 hrs. and in air at 600°      C. for two additional hours.                                             

The above data demonstrate that the pore size of the calcined product is greater than 6.2 Å.

    ______________________________________                                         (g) Example 44B (MgAPSO-46):                                                            Kinetic   Pressure  Temp  Wt. %                                       Adsorbate                                                                               Diameter, Å                                                                          (Torr)    (°C.)                                                                         Adsorbed*                                   ______________________________________                                         O.sub.2  3.46      100       -183  20.7                                        O.sub.2  3.46      734       -183  24.7                                        neopentane                                                                              6.2       100       24.5  8.4                                         isobutene                                                                               5.0       100       24    7.8                                         cyclo-hexane                                                                            6.0       59        23.7  11.9                                        H.sub.2 O                                                                               2.65      4.6       23    22.0                                        H.sub.2 O                                                                               2.65      20.0      23.6  27.4                                        ______________________________________                                          *calcined in nitrogen at 500° C. for 1.75 hours.                  

The above data demonstrate that the pore size of the calcined product is greater than about 6.2 Å.

    ______________________________________                                         (h) Example 104B (MgAPSO-47):                                                          Kinetic   Pressure   Temp  Wt. %                                       Adsorbate                                                                              Diameter, Å                                                                          (Torr)     (°C.)                                                                         Adsorbed*                                   ______________________________________                                         O.sub.2 3.46      99         -183  14.1                                        O.sub.2 3.46      725        -183  29.2                                        isobutane                                                                              5.0       100        22.8  0.2                                         n-hexane                                                                               4.3       49         23.3  4.2                                         H.sub.2 O                                                                              2.65      4.6        23.1  18.5                                        H.sub.2 O                                                                              2.65      17.8       22.9  28.7                                        ______________________________________                                          *calcined in air at 500° C. for 1.75 hrs.                         

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

EXAMPLE 110B

(a) MgAPSO-5, as prepared to in example 4B, was subjected to x-ray analysis. MgAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.35          11.71   83                                                       7.9*          11.19   (sh)                                                     12.8          6.92    11                                                       14.8          5.99    18                                                       15.8*         5.61    1                                                        16.4*         5.40    2                                                        19.0*         4.67    (sh)                                                     19.65         4.52    48-52                                                    21.0          4.23    54                                                       22.2          4.004   1                                                        23.6*         3.770   4                                                        24.7          3.604   4                                                        25.75         3.460   31                                                       27.2*         3.278 3                                                          28.9          3.089   20                                                       29.8          2.998   18                                                       31.8*         2.814   1                                                        33.5          2.675   5                                                        34.4          2.607   17                                                       36.8          2.442   4                                                        37.6          2.392   11                                                       40.7          2.217   1                                                        41.3          2.186   3                                                        42.05         2.149   4                                                        42.85         2.110   3                                                        43.4          2.085   2                                                        44.8          2.023   2                                                        45.4          1.998   2                                                        47.4          1.918   6                                                        51.1          1.787   2                                                        51.7          1.768   2                                                        52.4          1.746   1                                                        55.2          1.664   4                                                        ______________________________________                                          *impurity peak                                                           

(b) A portion of the as-synthesized MgAPSO-5 of part (a) was calcined in air at 600° C. for about 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         7.4            11.95   94                                                      7.9**          11.19   sh                                                      8.2**          10.78   sh                                                      12.9           6.86    20                                                      14.9           5.95    8                                                       16.4**         5.40    2                                                       19.3**         4.60    sh                                                      19.8           4.48    33                                                      21.1           4.21    52                                                      22.4           3.969   100                                                     24.8           3.590   4                                                       26.0           3.427   27                                                      27.1**         3.290   2                                                       27.9**         3.198   2                                                       28.3*          3.154   2                                                       29.1           3.069   20                                                      30.15          2.964   15                                                      33.7           2.660   5                                                       34.6           2.592   18                                                      37.0           2.430   4                                                       37.8           2.380   10                                                      41.6           2.171   1                                                       42.4           2.132   1                                                       42.9           2.108   1                                                       43.6           2.076   1                                                       45.0           2.015   1                                                       46.2           1.965   1                                                       47.8           1.903   4                                                       50.9           1.794   1                                                       51.6           1.771   1                                                       55.8           1.648   2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The MgAPSO-5 compositions are generally characterized by the data in Table IX-B below:

                  TABLE IX-B                                                       ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.2-7.4      12.28-11.95                                                                              m-vs                                                     14.6-14.95  6.07-5.93 w-m                                                     19.4-19.8    4.58-4.48 m                                                       20.85-21.1   4.26-4.21 vw-vs                                                   22.15-22.4   4.01-3.97 m-vs                                                     25.6-25.95  3.480-3.434                                                                              m                                                       ______________________________________                                    

(d) The MgAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table X-B, below:

                  TABLE X-B                                                        ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         7.2-7.4        12.28-11.95                                                                               69-100                                               12.65-12.9     7.00-6.86  8-12                                                  14.6-14.95    6.07-5.93 15-35                                                 19.4-19.8      4.58-4.48 38-73                                                 20.85-21.1     4.26-4.21 (sh)-100                                              22.15-22.4     4.013-3.969                                                                               48-100                                                24.4-24.85    3.648-3.583                                                                               0-14                                                  25.6-25.95    3.480-3.434                                                                              23-44                                                 28.7-29.1      3.110-3.069                                                                              12-20                                                 29.65-30.15    3.013-2.964                                                                              15-21                                                  33.4-33.75    2.683-2.656                                                                               2-11                                                  34.2-34.65    2.622-2.589                                                                              11-19                                                 37.4-37.8      2.405-2.380                                                                               5-11                                                 40.6-40.7      2.222-2.217                                                                              0-1                                                   41.1-41.6      2.196-2.171                                                                              0-3                                                   41.85-42.4     2.159-2.132                                                                              3-4                                                    42.6-43.05    2.122-2.101                                                                              0-3                                                   43.2-43.5      2.094-2.080                                                                              0-2                                                   44.6-45.0      2.032-2.015                                                                              0-2                                                   45.3-45.6      2.002-1.989                                                                              0-2                                                    46.1-46.35    1.969-1.959                                                                              0-1                                                    47.2-47.75    1.926-1.905                                                                              4-6                                                   50.4           1.811     0-1                                                   50.9-51.1      1.794-1.787                                                                              0-3                                                   51.6-51.9      1.771-1.762                                                                              0-4                                                   52.2-52.4      1.752-1.746                                                                              0-1                                                   55.2-55.8      1.664-1.648                                                                              0-4                                                   ______________________________________                                    

EXAMPLE 111-B

(a) MgAPSO-11, as prepared to in example 17B, was subjected to x-ray analysis. MgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         7.3**          12.11   47                                                      8.0            8.04    19                                                      9.3            9.51    30                                                      12.8**         6.92    (sh)                                                    13.1           6.76    13                                                      14.75**        6.01    6                                                       15.6           5.68    20                                                      16.1           5.51    3                                                       18.8           4.72    3                                                       19.6**         4.53    15                                                      20.25          4.39    32                                                      21.0*          4.23    100                                                     22.0           4.040   (sh)                                                    22.3**         3.987   57                                                      22.6           3.934   (sh)                                                    23.0           3.867   46                                                      24.4**         3.648   sh                                                      24.6           3.619   9                                                       25.7**         3.467   11                                                      26.3           3.389   20                                                      28.5**         3.132   11                                                      28.85          3.095   11                                                      29.35*         3.043   4                                                       29.8           2.998   9                                                       31.4           2.849   6                                                       32.7           2.739   13                                                      34.1           2.629   10                                                      34.3**         2.614   sh                                                      36.2**         2.481   4                                                       37.6*          2.392   12                                                      39.3           2.293   3                                                       40.6           2.222   1                                                       41.9*          2.156   2                                                       42.9           2.108   4                                                       44.6           2.032   3                                                       54.4           1.687   1                                                       ______________________________________                                          *Peak may contain impurity                                                     **Impurity peak                                                          

(b) A portion of the as-synthesized MgAPSO-11 of part (a) was calcined in air at 600° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.4*          11.95   30                                                       8.1           10.92   35                                                       9.6           9.21    35                                                       13.0          6.81    19                                                       15.8          5.61    30                                                       18.2*         4.87    4                                                        19.7*         4.51    9                                                        20.15         4.41    22                                                       21.2          4.19    100                                                      22.3          3.987   74                                                       22.9          3.883   sh                                                       23.35         3.810   43                                                       26.0*         3.427   sh                                                       26.3          3.389   17                                                       26.7          3.339   sh                                                       28.8          3.100   sh                                                       29.0*         3.079   17                                                       29.5          3.028   9                                                        30.0*         2.979   4                                                        31.0*         2.885   3                                                        31.7          2.823   15                                                       32.6          2.747   15                                                       33.8          2.652   3                                                        34.1*         2.629   15                                                       36.2          2.481   12                                                       37.9          2.374   15                                                       43.2          2.094   4                                                        ______________________________________                                          *Impurity peak                                                           

(c) The MgAPSO-11 compositions are generally characterized by the data of Table XI-B below:

                  TABLE XI-B                                                       ______________________________________                                         2Θ     d, (Å)                                                                              Relative Intensity                                       ______________________________________                                         9.0-9.6      9.83-9.21                                                                               vw-m                                                     20.8-21.2    4.27-4.19                                                                               vs                                                       22.0-22.4    4.04-3.97                                                                               vw-m                                                     22.4-22.8    3.97-3.90                                                                               vw-vs                                                    22.8-23.1    3.90-3.85                                                                               m                                                        ______________________________________                                    

(d) The MgAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-B, below:

                  TABLE XII-B                                                      ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                          7.8-8.15      11.33-10.85                                                                              sh-35                                                 9.0-9.6        9.83-9.21  6-60                                                 12.9-13.2      6.86-6.71 sh-22                                                 15.4-15.9      5.75-5.57 sh-30                                                 15.95-16.35    5.56-5.42 sh-3                                                  18.7-19.1      4.75-4.65 0-4                                                   20.0-20.5      4.44-4.33 sh-38                                                 20.8-21.2      4.27-4.19 100                                                   22.0-22.4      4.040-3.969                                                                              sh-72                                                 22.4-22.8      3.969-3.900                                                                              sh-90                                                 22.8-23.1      3.900-3.850                                                                              21-48                                                 23.35          3.810     0-4                                                   24.4-24.9      3.648-3.576                                                                              0-9                                                   26.2-26.7      3.401-3.339                                                                               0-21                                                 28.4-28.8      3.143-3.100                                                                              sh-17                                                 29.3-29.5      3.048-3.028                                                                              0-6                                                   29.6-30.0      3.018-2.979                                                                               0-17                                                 31.2-31.7      2.867-2.823                                                                               0-15                                                 32.4-32.8      2.763-2.730                                                                               0-18                                                 33.8-34.5      2.652-2.600                                                                               9-13                                                 35.7           2.515     0-3                                                   36.1-36.8      2.488-2.442                                                                               0-11                                                 37.5-37.9      2.398-2.374                                                                               0-17                                                 39.15-39.6     2.301-2.276                                                                              0--3                                                  40.25-40.75    2.241-2.214                                                                              0-1                                                   41.2-41.4      2.191-2.181                                                                              0-1                                                   41.8-42.1      2.161-2.146                                                                              0-4                                                   42.8-43.2      2.113-2.094                                                                              0-5                                                   44.5-44.9      2.036-2.019                                                                              0-4                                                   50.3-50.7      1.814-1.801                                                                              0-3                                                   54.4-54.6      1.687-1.681                                                                              0-3                                                   ______________________________________                                    

EXAMPLE 112B

(a) MgAPSO-16, as prepared to in example 93B, was subjected to x-ray analysis. MgAPSO-16 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         8.6**          10.30   13                                                      10.95**        8.10    36                                                      11.45          7.73    64                                                      13.3**         6.66    24                                                      15.85**        5.60    6                                                       17.25**        5.14    50                                                      17.75**        4.99    9                                                       18.7           4.74    45                                                      20.4**         4.35    35                                                      20.75**        4.28    10                                                      21.1**         4.21    26                                                      21.55**        4.12    sh                                                      21.85*         4.07    100                                                     23.05*         3.858   26                                                      26.3**         3.391   5                                                       26.75*         3.332   25                                                      28.45**        3.135   17                                                      28.65**        3.116   18                                                      29.0*          3.079   17                                                      29.9           2.987   20                                                      32.0**         2.796   30                                                      32.85          2.727   3                                                       34.6**         2.592   6                                                       34.85          2.573   4                                                       35.65**        2.519   12                                                      37.9*          2.373   8                                                       39.95*         2.256   5                                                       42.0**         2.152   4                                                       42.9**         2.108   4                                                       44.3*          2.044   4                                                       48.55*         1.876   10                                                      49.35**        1.846   5                                                       51.4**         1.778   5                                                       52.2**         1.752   2                                                       52.5           1.743   2                                                       55.0**         1.670   5                                                       ______________________________________                                          *Peak may contain impurity                                                     **Impurity peak                                                          

(b) A portion of the as-synthesized MgAPSO-16 of part (a) was calcined in air at 600° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 I/Io                                                ______________________________________                                         8.7**          10.16   25                                                      11.0**         8.04    185                                                     11.4           7.76    sh                                                      13.6**         6.51    200                                                     17.5**         5.07    50                                                      18.7           4.75    10                                                      21.2**         4.23    45                                                      22.2*          4.004   100                                                     22.8*          3.900   15                                                      23.7**         3.754   30                                                      25.1**         3.548   15                                                      26.4**         3.376   15                                                      27.3*          3.267   40                                                      28.7**         3.110   65                                                      29.0*          3.079   sh                                                      29.7           3.008   45                                                      32.0**         2.797   15                                                      32.6**         2.747   50                                                      33.2           2.706   sh                                                      34.6*          2.592   10                                                      35.6**         2.522   5                                                       ______________________________________                                          *Peak may contain impurity                                                     **Impurity peak                                                          

(c) The MgAPSO-16 compositions are characterized by the data of Table XIII-B below:

                  TABLE XIII-B                                                     ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         11.4-11.5    7.76-7.69 m                                                       18.7-18.8    4.75-4.72 w-m                                                     21.85-22.2   4.07-4.00 vs                                                      22.8-23.3    3.900-3.818                                                                              w-m                                                     26.75-27.3   3.332-3.267                                                                              w-m                                                     29.7-29.9    3.008-2.988                                                                              w-m                                                     ______________________________________                                    

(d) The MgAPSO-16 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-B, below:

                  TABLE XIV-B                                                      ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         11.5-11.5     7.76-7.69 sh-64                                                  18.7-18.8     4.75-4.72 10-45                                                  21.85-22.2    4.07-4.00 100                                                    22.8-23.3     3.900-3.818                                                                              15-26                                                  26.75-27.3    3.332-3.267                                                                              16-40                                                  28.95-29.0    3.084-3.079                                                                              sh-17                                                  29.7-29.9     3.008-2.988                                                                               9-45                                                  32.8-33.2     2.730-2.968                                                                              sh-3                                                    34.6-34.85   2.592-2.573                                                                               4-10                                                  37.8-38.0     2.380-2.368                                                                              4-7                                                     39.4-39.95   2.287-2.256                                                                              2-5                                                    44.3-44.5     2.044-2.036                                                                               2-10                                                  48.55-48.6    1.876-1.873                                                                               7-10                                                  52.4-52.5     1.746-1.743                                                                              1-2                                                    ______________________________________                                    

EXAMPLE 113B

(a) MgAPSO-20, as prepared in example 98B, was subjected to x-ray analysis. MgAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         13.9          6.36    44                                                       19.75         4.50    42                                                       22.05         4.029   3                                                        24.2          3.676   100                                                      28.0          3.184   12                                                       31.4          2.849   10                                                       34.5          2.601   14                                                       37.35         2.408   1                                                        38.45*        2.340   1                                                        40.0          2.253   4                                                        42.55         2.124   5                                                        47.3          1.921   4                                                        49.0*         1.859   1                                                        49.4*         1.846   2                                                        51.7          1.768   8                                                        ______________________________________                                          *impurity peak                                                           

(b) A portion of the as-synthesized MgAPSO-20 of part (a) was calcined in air at 600° C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         14.15         7.27    100                                                      20.05         4.43    20                                                       22.45         3.964   4                                                        24.6          3.616   54                                                       28.5          3.132   15                                                       32.0          2.799   10                                                       35.0          2.564   10                                                       ______________________________________                                    

(c) The MgAPSO-20 compositions are characterized by the data of Table XV-B below:

                  TABLE XV-B                                                       ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         13.8-14.2    6.42-6.23 m-vs                                                     19.6-20.15  6.53-4.41 m                                                       24.1-24.7    3.695-3.603                                                                              m-vs                                                    27.9-28.6    3.198-3.121                                                                              w                                                        31.3-32.05  2.861-2.791                                                                              w                                                       34.35-35.0   2.610-2.601                                                                              w                                                       ______________________________________                                    

(d) The MgAPSO-20 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-B, below:

                  TABLE XVI-B                                                      ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         13.8-14.2     6.42-6.23  42-100                                                 19.6-20.15   4.55-4.41 22-43                                                  21.95-22.45   4.050-3.964                                                                              3-7                                                    24.1-24.7     3.695-3.603                                                                               56-100                                                27.9-28.6     3.198-3.121                                                                              11-15                                                   31.3-32.05   2.861-2.791                                                                              10-12                                                  34.35-35.0    2.610-2.601                                                                              10-16                                                   37.2-37.35   2.417-2.408                                                                              1-2                                                    39.9-40.0     2.260-2.253                                                                              3-4                                                     42.4-42.55   2.130-2.124                                                                              5                                                      47.15-47.3    1.927-1.921                                                                              4-5                                                    51.55-51.7    1.772-1.768                                                                              8                                                      ______________________________________                                    

EXAMPLE 114B

(a) MgAPSO-34, as prepared in example 68B, was subjected to x-ray analysis. MgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         9.5           9.32    100                                                      12.8          6.91    15                                                       14.1          6.30    15                                                       17.95         4.94    21                                                       20.5          4.32    92                                                       22.2          4.002   4                                                        23.0          3.864   5                                                        25.15         3.540   23                                                       25.8          3.455   18                                                       27.5          3.243   3                                                        28.3          3.151   4                                                        29.5          3.029   4                                                        30.5          2.932   33                                                       31.2          2.866   22                                                       31.6*         2.833   5                                                        32.25         2.775   3                                                        34.35         2.611   7                                                        38.6          2.332   2                                                        36.2          2.480   8                                                        39.6          2.277   4                                                        43.1          2.100   3                                                        47.5          1.915   4                                                        ______________________________________                                         48.9          1.862   6                                                        50.9          6.795   4                                                        53.0          1.727   4                                                        54.5          1.684   2                                                        55.75         1.649   4                                                        ______________________________________                                    

(b) A portion of the as-synthesized MgAPSO-34 of part (a) was calcined in air at 550° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         9.7           9.12    100                                                      13.1          6.76    22                                                       14.2          6.24    1                                                        16.3          5.44    15                                                       18.1          4.90    10                                                       19.3          4.60    3                                                        20.95         4.24    31                                                       21.6*         4.11    sh                                                       22.4          3.969   3                                                        23.35         3.809   3                                                        25.35         3.513   11                                                       26.3          3.389   10                                                       28.5          3.132   4                                                        30.0          2.979   sh                                                       31.0          2.885   23                                                       33.8          2.652   2                                                        35.0          2.564   3                                                        36.6          2.455   1                                                        43.7          2.071   1                                                        49.4          1.845   2                                                        51.3          1.781   2                                                        52.2          1.752   1                                                        53.1          1.725   1                                                        54.0          1.698   2                                                        ______________________________________                                          *impurity peak                                                           

(c) The MgAPSO-34 compositions are characterized by the data of Table XVII-B below:

                  TABLE XVII-B                                                     ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.3-9.7      9.51-9.12 vs                                                      15.8-16.3    5.61-5.44  w-m                                                    20.25-21.0   4.39-4.23  m-vs                                                   25.7-26.3    3.466-3.389                                                                              vw-m                                                    30.0-30.8    2.979-2.903                                                                              vw-m                                                    30.9-31.4    2.894-2.849                                                                               w-m                                                    ______________________________________                                    

(d) The MgAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-B below.

                  TABLE XVIII-B                                                    ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         9.3-9.7        9.51-9.12  99-100                                               12.6-13.1      7.03-6.76 11-25                                                 13.8-14.3      6.42-6.19  0-24                                                 15.8-16.3      5.61-5.44 13-56                                                 17.8-18.2      4.98-4.87  5-28                                                 19.1-19.4      4.65-4.58 0-3                                                   20.25-21.0     4.39-4.23  22-100                                               22.2-22.5      4.004-3.952                                                                              0-6                                                   22.8-23.4      3.900-3.802                                                                              0-6                                                   24.9-25.4      3.576-3.507                                                                               6-27                                                 25.7-26.3      3.466-3.389                                                                               6-29                                                 27.4-28.0      3.255-3.187                                                                              0-4                                                   28.2-28.8      3.164-3.100                                                                              0-4                                                   29.0-29.6      3.079-3.018                                                                              0-6                                                   30.0-30.8      2.979-2.903                                                                               0-34                                                 30.9-31.4      2.894-2.849                                                                              16-30                                                 32.2-32.4      2.780-2.763                                                                              0-4                                                   33.8-34.5      2.401-2.600                                                                               0-15                                                 34.6-35.0      2.592-2.564                                                                              0-4                                                   36.0-36.6      2.495-2.456                                                                              0-4                                                   38.4-39.0      2.344-2.309                                                                              0-2                                                   43.0-43.7      2.103-2.071                                                                              0-3                                                   44.6-45.0      2.032-2.015                                                                              0-1                                                   47.2-47.6      1.926-1.910                                                                              0-4                                                   48.3-49.4      1.884-1.845                                                                              0-6                                                   50.2           1.817     0-2                                                   50.7-51.4      1.801-1.778                                                                              0-4                                                   51.3-51.5      1.781.1.774                                                                              0-2                                                   52.9-53.1      1.731.1.725                                                                              0-4                                                   54.1-54.6      1.695-1.681                                                                              0-4                                                   55.5-55.9      1.656-1.645                                                                              0-4                                                   ______________________________________                                    

EXAMPLE 115B

(a) MgAPSO-35, as prepared in example 85B, was subjected to x-ray analysis. MgAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.6           10.28   11                                                      10.9           8.12    44                                                       11.4**        7.76    2                                                       13.4           6.61    20                                                      15.9           5.57    9                                                       17.3           5.13    80                                                      17.7           5.01    sh                                                       18.7**        4.75    1                                                       20.9           4.25    54                                                       21.9*         4.06    100                                                      22.7**        3.917   sh                                                       23.25         3.826   27                                                      24.9           3.576   6                                                       25.8           3.453   1                                                        26.85*        3.320   16                                                      27.1           3.290   sh                                                      28.3           3.153   44                                                      29.0           3.079   10                                                       31.45*        2.844   sh                                                      32.1           2.788   37                                                       32.4*         2.763   sh                                                       34.3*         2.614   7                                                        35.2**        2.550   1                                                       35.8           2.508   2                                                        37.6*         2.392   2                                                       39.4           2.287   1                                                       40.9           2.206   1                                                       41.8           2.161   4                                                       42.5           2.127   5                                                        44.5*         2.036   4                                                       47.5           1.914   2                                                        48.3*         1.884   4                                                       48.8           1.866   4                                                       49.4           1.845   5                                                       51.0           1.791   7                                                       55.2           1.664   4                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity                                                               

(b) A portion of the as-synthesized MgAPSO-35 of part (a) was calcined in air at 500° C. for about 68 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.5           10.40   21                                                      10.8           8.19    100                                                      11.3*         7.83    sh                                                      13.3           6.66    76                                                      15.8           5.61    3                                                       17.2           5.16    31                                                       20.15*        4.41    110                                                     20.8           4.27    sh                                                       21.25*        4.18    97                                                       21.85         4.07    40                                                       22.8*         3.900   43                                                      23.1           3.850   sh                                                       24.2*         3.678   6                                                       24.8           3.590   6                                                        26.2*         3.401   45                                                      27.0           3.302   10                                                      27.3           3.267   10                                                      28.3           3.153   24                                                      29.5           3.028   19                                                       30.9*         2.894   5                                                       31.4           2.849   7                                                       32.2           2.780   19                                                      32.7           2.739   sh                                                       33.8*         2.652   4                                                       34.4           2.607   5                                                        35.3*         2.543   21                                                      36.0           2.495   4                                                        37.2*         2.417   4                                                       38.4           2.344   6                                                       39.8           2.265   4                                                       40.9           2.206   2                                                       41.9           2.156   5                                                       42.6           2.122   6                                                        43.5*         2.085   3                                                       44.8           2.023   2                                                       45.1           2.010   4                                                       48.4           1.881   2                                                       49.3           1.848   2                                                       51.3           1.781   3                                                       55.5           1.656   5                                                       ______________________________________                                          *impurity peak                                                           

(c) The MgAPSO-35 compositions are generally characterized by the data of Table XIXB below:

                  TABLE XIXB                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         10.6-11.1    8.35-7.97 m-vs                                                    13.1-13.7    6.76-6.46 w-vs                                                    17.0-17.6    5.22-5.04 m-s.sup.                                                20.6-21.2    4.31-4.19 vw-m                                                    21.6-22.2    4.11-4.00 m-vs                                                    28.1-28.8    3.175-3.100                                                                              m                                                       ______________________________________                                    

(d) The MgAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-B, below:

                  TABLE XX-B                                                       ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         8.3-8.8        10.65-10.05                                                                              10-21                                                 10.6-11.1      8.35-7.97  36-100                                               13.1-13.7      6.76-6.46  17-100                                               15.7-16.0      5.64-5.54 0-9                                                   17.0-17.6      5.22-5.04 25-80                                                 17.7-17.8      5.01-4.98  0-sh                                                 20.6-21.2      4.31-4.19 sh-54                                                 21.6-22.2      4.11-4.00  40-100                                               23.0-23.7      3.867-3.754                                                                              sh-27                                                 24.6-25.2      3.619-3.534                                                                              5-8                                                   25.8-26.4      3.453-3.376                                                                              0-8                                                   26.6-27.3      3.351-3.267                                                                              10-16                                                 27.1           3.290     sh-10                                                 28.1-28.8      3.175-3.100                                                                              24-44                                                 28.9-29.7      3.089-3.008                                                                               5-23                                                 31.45-31.5     2.844-2.840                                                                              sh-7                                                  31.9-32.4      2.805-2.763                                                                              19-37                                                 32.4-32.7      2.763-2.739                                                                              sh                                                    34.1-34.7      2.629-2.585                                                                              5-9                                                   35.6-36.1      2.522-2.488                                                                              0-4                                                   37.1-38.0      2.404-2.368                                                                              0-6                                                   39.4-39.9      2.287-2.259                                                                              0-4                                                   40.8-40.9      2.212-2.206                                                                              0-1                                                   41.7-42.2      2.166-2.141                                                                              0-5                                                   42.2-42.7      2.132-2.118                                                                              0-6                                                   44.5-44.8      2.036-2.023                                                                              0-7                                                   45.0-45.1      2.014-2.010                                                                              0-1                                                   47.4-47.7      1.914-1.907                                                                              0-2                                                   48.2-48.6      1.888-1.873                                                                              0-4                                                   48.7-49.0      1.870- 1.859                                                                             0-4                                                   49.3-49.7      1.848-1.834                                                                              0-5                                                   50.8-51.5      1.797-1.774                                                                              0-7                                                   55.2-55.6      1.664-1.653                                                                              0-4                                                   ______________________________________                                    

EXAMPLE 116B

(a) MgAPSO-36, as prepared in example 5B, was subjected to x-ray analysis. MgAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                           7.4**        11.95   sh                                                       7.9           11.19   100                                                      8.1           10.92   sh                                                       12.8**        6.92    3                                                        13.45         6.58    6                                                         14.75**      6.01    4                                                       15.7           5.64    (sh)                                                    16.3           5.44    31                                                      18.9           4.70    41                                                       19.5**        4.55    7                                                        20.7*         4.29    49                                                       21.55         4.12    (sh)                                                    21.8           4.077   (sh)                                                     22.35*        3.978   42                                                      22.8           3.900   (sh)                                                    23.8           3.739   9                                                        25.7**        3.466   6                                                       27.1           3.290   14                                                      28.2           3.164   10                                                       28.9*         3.089   12                                                      30.1           2.969   7                                                       31.8           2.814   11                                                       33.0*         2.714   3                                                        34.6*         2.592   16                                                      35.7           2.515   4                                                        37.6*         2.349   3                                                       39.3           2.293   1                                                       40.1           2.249   3                                                       41.3           2.186   4                                                        42.0**        2.151   2                                                       43.0           2.103   2                                                       44.0           2.058   2                                                       45.3           2.002   1                                                       46.6           1.949   1                                                       47.3           1.922   3                                                       48.8           1.867   1                                                       51.1           1.787   2                                                       53.7           1.707   2                                                       55.4           1.659   3                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized MgAPSO-36 of part (a) was calcined in air at 500° C. for about 2 hours and at 600° C. for an additional 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         7.4**          11.95   sh                                                      7.9            11.19   100                                                     8.2            10.78   sh                                                      12.8**         6.92    3                                                       13.45          6.58    8                                                       14.9**         5.95    2                                                       15.9           5.57    sh                                                      16.5           5.37    24                                                      19.3           4.60    38                                                      19.75**        4.50    sh                                                      20.8           4.27    25                                                      21.2**         4.19    sh                                                      21.8           4.08    sh                                                      22.35          3.978   25                                                      22.6**         3.934   sh                                                      23.0           3.867   sh                                                      23.9           3.723   5                                                       24.9**         3.576   1                                                       25.8**         3.453   4                                                       27.2           3.278   16                                                      28.35          3.148   7                                                       29.1*          3.69    10                                                      29.9           2.988   3                                                       30.4*          2.940   5                                                       32.0           2.797   8                                                       33.2           2.698   1                                                       35.0*          2.564   7                                                       36.0           2.495   3                                                       37.7*          2.386   2                                                       39.5           2.281   1                                                       40.3           2.238   2                                                       41.3           2.186   4                                                       42.0**         2.151   2                                                       43.5           2.080   1                                                       44.3           2.045   1                                                       45.4           1.998   1                                                       47.6           1.910   3                                                       51.2           1.784   1                                                       55.5           1.656   1                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The MgAPSO-36 compositions are generally characterized by the data of Table XXI-B below:

                  TABLE XXI-B                                                      ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.8-8.0      11.33-11.05                                                                              vs                                                      16.3-16.5    5.44-5.37 m                                                       18.9-19.3    4.70-4.60 m                                                       20.7-20.8    4.29-4.27 m                                                       22.35        3.98      m                                                       ______________________________________                                    

(d) The MgAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-B below:

                  TABLE XXII-B                                                     ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         7.8-8.0        11.33-11.05                                                                              100                                                   8.1-8.2        10.92-10.78                                                                               0-sh                                                  13.45         6.58      6-8                                                   15.7-15.9      5.64-5.57 sh                                                    16.3-16.5      5.44-5.37 24-31                                                 18.9-19.3      4.70-4.60 38-41                                                 20.7-20.8      4.29-4.27 25-49                                                 21.0           4.23       0-sh                                                 21.55-21.8     4.12-4.08 sh                                                    21.8-21.9      4.077-4.058                                                                              sh                                                    22.35          3.978     25-42                                                 22.8-23.0      3.900-3.867                                                                              (sh)                                                  23.8-23.9      3.739-3.723                                                                              5-9                                                   27.1-27.2      3.290-3.278                                                                              14-16                                                  28.1-28.35    3.176-3.148                                                                               7-10                                                 28.8-29.1      3.100-3.069                                                                              10-12                                                 29.9-30.1      2.988-2.969                                                                              3-7                                                   31.8-32.0      2.814-2.797                                                                               8-11                                                 33.0-33.2      2.714-2.698                                                                              1-3                                                   34.6-35.0      2.592-2.564                                                                               7-16                                                 35.7-36.0      2.515-2.495                                                                              3-4                                                   37.6-37.7      2.392-2.386                                                                              2-3                                                   39.3-39.5      2.293-2.281                                                                              1                                                     40.1-40.3      2.249-2.238                                                                              2-3                                                   41.3           2.186     4                                                     43.0-43.5      2.103-2.080                                                                              1-2                                                   43.95-44.3     2.060-2.045                                                                              1-2                                                   45.2-45.4      2.006-1.998                                                                              1                                                     46.6           1.949     0-1                                                   47.3-47.6      1.922-1.910                                                                              3                                                     48.8           1.867     0-1                                                   51.1-51.2      1.787-1.784                                                                              1-2                                                   53.7           1.707     0-2                                                   55.3-55.5      1.661-1.656                                                                              1-3                                                   ______________________________________                                    

EXAMPLE 117B

(a) MgAPSO-39, as prepared in example 55B, was subjected to x-ray analysis. MgAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.1**         10.92   6                                                        8.5**         10.40   15                                                       8.9**         9.98    1                                                        9.45*         9.34    30                                                      12.4**         7.13    2                                                       13.4*          6.60    48                                                      14.2**         6.22    2                                                       14.4**         6.15    2                                                       14.6**         6.06    2                                                       15.65**        5.66    4                                                       18.15          4.89    33                                                      20.3**         4.38    17                                                      21.3*          4.18    70                                                      22.1**         4.027   13                                                      22.6*          3.929   100                                                     23.15**        3.844   10                                                      26.4**         3.375   3                                                       27.0           3.301   4                                                       27.8**         3.208   3                                                       28.0*          3.191   4                                                       28.7*          3.113   9                                                       29.7           3.007   13                                                      30.3           2.953   25                                                      31.7**         2.823   5                                                       32.7           2.736   12                                                      34.1*          2.632   7                                                       35.1**         2.555   2                                                       36.7*          2.448   2                                                       38.1*          2.361   9                                                       39.25**        2.295   2                                                       41.0           2.200   2                                                       43.3           2.089   2                                                       43.8           2.067   1                                                       45.0           2.015   1                                                       46.2*          1.966   2                                                       47.2*          1.926   1                                                       48.8           1.867   4                                                       49.4           1.845   3                                                       51.45*         1.776   4                                                       52.3           1.749   2                                                       54.55          1.683   2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The MgAPSO-39 compositions are generally characterized by the data of Table XXIII-B below:

                  TABLE XXIII-B                                                    ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.2-9.6      9.61-9.21 m                                                       13.1-13.5    6.76-6.56 m                                                       17.8-18.3    4.98-4.85 m                                                       20.8-21.3    4.27-4.17 m-vs                                                    22.2-22.8    4.00-3.90 vs                                                      30.0-30.3    2.979-2.950                                                                              w-m                                                     ______________________________________                                    

(c) The MgAPSO-39 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-B below.

                  TABLE XXIV-B                                                     ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         9.2-9.6        9.61-9.21 20-53                                                 13.1-13.5      6.76-6.56 25-53                                                 17.8-18.3      4.98-4.85 23-34                                                 20.8-21.3      4.27-4.17  79-100                                               22.2-22.8      4.002-3.900                                                                               97-100                                                26.8-27.05    3.326-3.296                                                                              3-4                                                   28.0-28.2      3.191-3.175                                                                              0-4                                                   28.6-28.8      3.121-3.100                                                                              sh-17                                                 29.4-29.8      3.038-2.998                                                                              13-20                                                 30.0-30.3      2.979-2.950                                                                              17-29                                                 32.4-32.8      2.763-2.730                                                                              10-16                                                 33.9-34.2      2.644-2.622                                                                              sh-11                                                  36.7-36.85    2.448-2.439                                                                              0-2                                                   37.8-38.1      2.380-2.362                                                                              5-9                                                   40.7-41.0      2.217-2.201                                                                              0-5                                                   43.0-43.4      2.103-2.085                                                                              0-2                                                   45.0           2.014     0-1                                                   46.2-46.3      1.966-1.961                                                                              0-2                                                   47.2-47.3      1.926-1.922                                                                              0-1                                                    48.5-48.85    1.877-1.864                                                                              4-5                                                   49.0-49.5      1.859-1.841                                                                              0-3                                                   51.0-51.5      1.791-1.778                                                                              3-5                                                   52.1-52.4      1.755-1.746                                                                              0-4                                                   54.2-54.6      1.692-1.681                                                                              0-2                                                   ______________________________________                                    

EXAMPLE 118B

(a) MgAPSO-43, as prepared in example 92B, was subjected to x-ray analysis. MgAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         6.5*           13.63   8                                                       7.6**          11.66   35                                                      23.3           7.20    100                                                     13.05**        6.77    4                                                       14.45**        6.14    4                                                       15.15*         5.85    2                                                       16.5**         5.37    3                                                       17.3           5.13    12                                                      19.7*          4.51    3                                                       20.35**        4.37    2                                                       21.45*         4.14    49                                                      22.65**        3.928   6                                                       34.9**         3.726   3                                                       24.0           3.701   3                                                       24.35          3.653   2                                                       26.7*          3.336   7                                                       27.6           3.232   39                                                      28.05*         3.182   18                                                      28.55*         3.126   5                                                       29.65**        2.013   1                                                       30.95**        2.889   2                                                       32.8**         2.729   7                                                       33.05          2.710   8                                                       35.8*          2.510   3                                                       38.3**         2.350   2                                                       39.55**        2.278   1                                                       43.75**        2.070   2                                                       44.05**        2.055   1                                                       45.4           1.997   3                                                       45.65**        1.998   3                                                       49.0**         1.859   3                                                       51.1*          1.788   4                                                       52.0*          1.759   1                                                       53.0           1.728   3                                                       53.7           1.707   2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized MgAPSO-43 of part (a) was calcined in air at 500° C. for about 1 hour and at 600° C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          6.95*         12.73   30                                                       8.15*         10.87   47                                                      12.95          6.83    35                                                      17.4           5.10    10                                                      17.4           5.10    10                                                      21.45          4.14    100                                                     23.2*           3.832  44                                                      28.15           3.167  25                                                      ______________________________________                                          *impurity peak                                                           

(c) The MgAPSO-43 compositions are generally characterized by the data of Table XXV-B below:

                  TABLE XXV-B                                                      ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         12.3-12.95   7.20-6.83 m-vs                                                    17.3-17.45   5.13-5.09 w                                                       21.45-21.6   4.15-4.12 m-vs                                                    27.6-27.75   3.232-3.215                                                                              m                                                       33.05-33.2   2.710-2.699                                                                              w                                                       ______________________________________                                    

(d) The MgAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-B below:

                  TABLE XXVI-B                                                     ______________________________________                                         2Θ     d, (Å)                                                                               100 × I/Io                                        ______________________________________                                         12.3-12.95   7.20-6.83  35-100                                                 15.15-15.5   5.85-5.37 2-4                                                     17.3-17.45   5.13-5.09 12                                                      19.7-19.85   4.51-4.47 3-5                                                     21.45-21.6   4.15-4.12  49-100                                                 24.35-24.5   3.653-3.635                                                                              2                                                       26.7-26.85   3.336-3.319                                                                              7-9                                                     27.6-27.75   3.232-3.215                                                                              39-50                                                   28.05-28.2   3.182-3.165                                                                              18-25                                                   28.55-28.75  3.126-3.107                                                                              5-6                                                     33.05-33.2   2.710-2.699                                                                               8-12                                                   35.8-35.9    2.510-2.502                                                                              3-4                                                     45.4-45.55   1.997-1.991                                                                              3                                                       51.1-51.2    1.788-1.785                                                                              4                                                       52.0-52.25   1.759-1.750                                                                              1-2                                                     53.0-53.1    1.728-1.725                                                                              3-4                                                     53.7-53.95   1.707-1.700                                                                              2                                                       ______________________________________                                    

EXAMPLE 119B

(a) MgAPSO-44, as prepared in example 88B, was subjected to X-ray analysis. MgAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                           6.7**        13.19   64                                                        7.3**        12.11   12                                                       9.35          9.46    100                                                      12.95*        6.84    16                                                      13.7           6.46    2                                                       4.5            6.11    5                                                        14.8**        5.99    3                                                       16.1           5.54    35                                                      17.3           5.13    7                                                       18.9           4.70    8                                                        19.6**        4.53    9                                                       20.7           4.29    100                                                      20.9**        4.25    sh                                                      21.7           4.10    13                                                       22.3**        3.986   28                                                      22.5           3.952   sh                                                      23.0           3.867   7                                                       24.3           3.663   37                                                       25.8**        3.453   sh                                                      26.1           3.414   7                                                       27.5           3.243   10                                                       28.8**        3.998   4                                                       29.6           3.018   sh                                                       29.9*         2.988   15                                                      30.7           2.912   48                                                      31.4           2.849   1                                                       32.4           2.763   4                                                       32.7           2.739   3                                                        33.4**        2.683   1                                                        34.3**        2.614   3                                                       34.8           2.578   4                                                       35.4           2.536   6                                                       36.8           2.442   1                                                        37.5**        2.398   3                                                       38.4           2.344   1                                                       39.1           2.304   1                                                       39.8           2.265   1                                                        42.0*         2.146   6                                                       43.4           2.085   2                                                       46.5           1.957   1                                                       47.1           1.929   3                                                        48.0*         1.895   8                                                       48.5           1.877   5                                                       50.1           1.821   10                                                      51.8           1.768   1                                                       53.6           1.710   10                                                      54.6           1.6871  1                                                       55.3**         1.661   1                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized MgAPSO-44 of part (a) was calcined in air for 2.5 hours at 500° C. and then for 0.25 hour at 600° C. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                           2.9**        30.46   8                                                         7.35**       12.03   64                                                        8.9**        9.94    sh                                                        9.1**        9.72    sh                                                       9.5           9.31    100                                                      12.8*         6.92    35                                                      13.9           6.37    4                                                        14.7**        6.07    3                                                       16.0           5.54    20                                                      17.8           4.98    53                                                       19.6**        4.53    14                                                      20.6           4.31    82                                                       21.1**        4.21    16                                                       22.3*         3.986   sh-28                                                   23.0           3.867   7-8                                                      25.0*         3.562   18                                                       25.8*         3.453   17                                                      27.6           3.232   1                                                       28.2           3.164   3                                                        28.9**        3.089   4                                                       29.8           2.998   4                                                        30.5*         2.931   24                                                      31.0           2.885   16                                                      31.6           2.831   sh                                                      32.2           2.780   1                                                       33.2           2.698   sh                                                       33.5**        2.675   3                                                        34.3**        2.614   8                                                       34.8           2.578   1                                                       36.0           2.494   3                                                        37.7**        2.386   2                                                       38.5           2.338   1                                                       39.0           2.309   1                                                       39.6           2.276   3                                                        42.0*         2.151   1                                                        4.9**         2.108   2                                                       43.3           2.090   1                                                        47.5*         1.918   4                                                       48.8           1.866   3                                                       50.8           1.797   4                                                       51.6           1.771   1                                                       53.0           1.728   4                                                        54.3**        1.689   1                                                       55.6           1.656   1                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The MgAPSO-44 compositions are generally characterized by the data of Table XXVII-B below:

                  TABLE XXVII-B                                                    ______________________________________                                         2Θ    d, (Å)      100 ×I/Io                                    ______________________________________                                          9.2-9.45   9.61-9.37       vs                                                 15.9-16.1   5.57-5.50       m                                                  17.2-18.0   5.16-4.93       vw-m                                                20.5-20.75 4.33-4.28       m-vs                                               24.3-25.0   3.663-3.562     w-m                                                30.5-31.0   2.931-2.885     w-m                                                ______________________________________                                    

(d) the MgAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have pattens which are characterized by the x-ray powder diffraction shown in Table XXVIII-B below:

                  TABLE XXVIII-B                                                   ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                          9.2-9.45      9.61-9.37 100                                                    12.8-13.0*    6.92-6.81 11-35                                                 13.6-14.0      6.51-6.33 2-4                                                   14.5-14.6      6.11-6.07 0-5                                                   15.9-16.1      5.57-5.50 20-36                                                 17.2-18.0      5.16-4.93 7                                                     18.8-19.0      4.72-4.67  7-53                                                  20.5-20.75    4.33-4.28  58-100                                               21.7-21.8      4.10-4.08  0-18                                                 22.3-22.6      3.986-3.924                                                                              sh                                                    23.0-23.3      3.867-3.817                                                                              8                                                      24.3-25.0*    3.663-3.562                                                                              17-58                                                  25.8-26.15*   3.453-3.406                                                                              10-18                                                 27.5-27.8      3.243-3.209                                                                               1-12                                                 28.2           3.175     0-3                                                   29.6-29.8      3.018-2.998                                                                              0-sh                                                   29.7-30.5*    3.008-2.931                                                                               4-15                                                 30.5-31.0      2.931-2.885                                                                              16-48                                                 31.4-31.6      2.849-2.831                                                                              sh-1                                                  32.2-32.5      2.780-2.755                                                                              1-5                                                   32.7-33.2      2.739-2.698                                                                              sh-3                                                  34.8           3.578     0-1                                                   35.3-36.0      2.543-2.495                                                                              3-6                                                   36.8           2.442     0-1                                                   38.4-39.1      2.344-2.338                                                                              0-1                                                   39.0-39.1      2.309-2.304                                                                              0-1                                                   39.6-40.0      2.276-2.254                                                                              0-1                                                    42.0-42.2*    2.151-2.141                                                                              0-6                                                   43.3-43.6      2.090-2.076                                                                              0-2                                                   46.5           1.953     0-1                                                   47.1- 47.5     1.929-1.914                                                                              0-5                                                    48.0-48.2*    1.895-1.888                                                                              0-8                                                   48.5-48.8      1.877-1.866                                                                              0-5                                                   50.0-50.8      1.824-1.797                                                                               4-10                                                 51.6-51.8      1.771-1.765                                                                              0-1                                                   53.0-53.8      1.728-1.704                                                                               4-10                                                 54.3-54.6      1.689-1.681                                                                              0-2                                                   ______________________________________                                          *peak may contain impurity                                               

EXAMPLE 120B

(a) MgAPSO-46, as prepared in example 44B, was subjected to x-ray analysis. MgAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         6.6           13.44   3                                                        7.7           11.48   100                                                      10.1          8.76    <1                                                       12.4          7.15    2                                                        13.2          6.71    2                                                        13.75         6.44    3                                                        14.9          5.95    1                                                        15.3          5.79    2                                                        16.6          5.33    3                                                        17.4          5.10    <1                                                       19.8          4.48    1                                                        20.45         4.34    4                                                        20.7          4.29    sh                                                       21.5          4.13    12                                                       22.75         3.906   6                                                        24.2          3.682   3                                                        25.2          3.534   <1                                                       26.85         3.320   4                                                        27.7          3.219   3                                                        28.2          2.163   2                                                        28.7          3.109   4                                                        29.8          3.000   1                                                        31.1          2.873   2                                                        31.7          2.823   <1                                                       32.9          2.722   <1                                                       34.2          2.622   1                                                        35.85         2.505   2                                                        36.5          2.462   <1                                                       37.2          2.417   <1                                                       38.4          2.344   <1                                                       39.6          2.276   <1                                                       41.0          2.201   <1                                                       42.2          2.141   <1                                                       43.9          2.062   1                                                        45.9          1.977   <1                                                       47.5          1.914   <1                                                       49.4          1.845   <1                                                       50.1          1.821   <1                                                       51.4          1.778   <1                                                       52.2          1.752   <1                                                       ______________________________________                                    

(b) A portion of the as-synthesized MgAPSO-46 of part (a) was calcined in nitrogen at 500° for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         6.8           13.0    8                                                        7.8           11.33   100                                                      13.5          6.56    8                                                        14.0          6.33    3                                                        15.2          5.83    9                                                        15.6          5.68    sh                                                       16.95         5.23    11                                                       20.2          4.40    sh                                                       20.7          4.29    6                                                        21.7          4.10    10                                                       23.0          3.867   6                                                        24.4          3.648   3                                                        27.2          3.278   4                                                        27.9          3.198   3                                                        28.4          3.143   sh                                                       28.9          3.089   6                                                        30.2          2.959   2                                                        31.4          2.849   3                                                        32.0          2.797   1                                                        33.4          2.683   2                                                        34.2          2.622   2                                                        36.2          2.481   2                                                        37.0          2.430   <1                                                       40.2          2.243   <1                                                       41.3          2.186   1                                                        44.2          2.049   1                                                        46.3          1.961   <1                                                       47.9          1.899   <1                                                       50.5          1.807   1                                                        51.9          1.762   <1                                                       52.6          1.740   <1                                                       ______________________________________                                    

(c) The MgAPSO-46 compositions are generally characterized by the data of Table XXIX-B below:

                  TABLE XXIX-B                                                     ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.2-8.1      12.28-10.92                                                                              vs                                                      21.2-21.8    4.19-4.08 w-m                                                     22.5-23.0    3.952-3.867                                                                              vw-m                                                    26.6-27.2    3.351-3.278                                                                              vw-w                                                    28.5-29.0    3.132-3.079                                                                              vw-w                                                    ______________________________________                                    

(d) The MgAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXX-B below:

                  TABLE XXX-B                                                      ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         6.5-6.9        13.60-12.81                                                                               3-10                                                 7.2-8.1        12.28-10.92                                                                              100                                                    9.8-10.3      9.03-8.59 0-1                                                   12.4           7.14      0-4                                                   12.9-13.5      6.86-6.56 2-8                                                   13.5-14.0      6.56-6.33 3-8                                                   14.8-15.2      5.99-5.83 1-9                                                   15.2-15.8      5.83-5.61 (sh)-5                                                16.5-17.6      5.37-5.04  3-11                                                 17.3-17.4      5.13-5.10 0-1                                                   19.7-20.2      4.51-4.40 (sh)-5                                                20.3-20.7      4.37-4.29 4-9                                                   21.2-21.8      4.19-4.08 10-36                                                 22.5-23.0      3.952-3.867                                                                               6-20                                                 23.7-24.4      3.754-3.648                                                                               3-11                                                 25.0-25.5      3.562-3.648                                                                              0-1                                                   26.6-27.2      3.351-3.278                                                                               4-17                                                 27.5-27.9      3.243-3.198                                                                               3-12                                                 28.0-28.4      3.255-3.143                                                                              sh-2                                                  28.5-29.0      3.132-3.079                                                                               4-15                                                 29.6-30.2      3.018-2.959                                                                              1-4                                                   30.9-31.4      2.894-2.849                                                                              2-6                                                   31.6-32.0      2.831-2.797                                                                              1-3                                                   32.6-33.4      2.747-2.683                                                                              1-2                                                   33.95-34.4     2.640-2.607                                                                              1-4                                                   35.7-36.2      2.515-2.481                                                                              2-6                                                   36.3-37.0      2.475-2.430                                                                              0-2                                                   37.0-37.6      2.430-2.392                                                                              0-1                                                   37.9-38.4      2.374-2.344                                                                              0-1                                                   39.5- 40.2     2.281-2.243                                                                              0-1                                                   40.7-41.3      2.217-2.186                                                                              0-1                                                   43.7-44.3      2.071-2.45                                                                               0-1                                                   45.8-46.4      1.981-1.957                                                                              0-1                                                   47.3-47.9      1.922-1.899                                                                              0-1                                                   49.2-49.3      1.852-1.848                                                                              0-1                                                   49.9-50.5      1.828-1.807                                                                              0-1                                                   51.2-51.9      1.784-1.762                                                                              0-1                                                   52.1-52.6      1.755-1.740                                                                              0-1                                                   ______________________________________                                    

EXAMPLE 121-B

(a) MgAPSO-47, as prepared in example 104B, was subjected to x-ray analysis. MgAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          9.5           9.29    100                                                      12.95         6.84    9                                                       13.9           6.36    5                                                        16.05         5.52    22                                                       17.65         5.03    9                                                        19.05         4.66    2                                                        20.65         4.30    53                                                      21.9           4.06    7                                                        22.45*        3.961   2                                                        23.05         3.859   7                                                        24.75         3.598   21                                                       25.95         3.432   12                                                      27.7           3.222   5                                                        27.95         3.190   3                                                        28.55*        3.126   1                                                        29.55         3.022   3                                                       30.6           2.919   21                                                      30.9           2.893   sh                                                      31.5           2.837   2                                                       32.4           2.763   1                                                        33.25         2.695   2                                                        34.55         2.597   4                                                        34.95         2.567   1                                                       35.8           2.510   3                                                       38.5           2.338   2                                                       39.1           2.305   1                                                       39.7           2.270   2                                                       42.5           2.126   2                                                       43.4           1.085   1                                                       47.7           1.907   2                                                       48.7           1.870   4                                                       50.4           1.810   3                                                       51.7           1.768   1                                                        52.45         1.745   1                                                       53.3           1.719   2                                                       54.1           1.695   1                                                       54.6           1.681   1                                                       55.9           1.645   2                                                       ______________________________________                                          *Impurity peak                                                           

(b) A portion of the as-synthesized MgAPSO-47 of part (a) was calcined in air at 500° C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          9.65          9.17    100                                                      13.05         6.79    20                                                      14.2           6.25    4                                                       16.2           5.46    14                                                      18.0           4.92    11                                                      19.3           4.60    3                                                        20.85         4.26    33                                                      22.3           3.980   2                                                        22.6*         3.933   3                                                       23.3           3.819   4                                                        23.6*         3.771   1                                                        24.55*        3.626   2                                                        25.25         3.556   12                                                      26.2           3.400   10                                                      28.0           3.188   2                                                       28.5           3.132   4                                                        29.95         2.983   2                                                        30.95         2.889   15                                                      31.4           2.849   sh                                                      34.8           2.575   3                                                       36.5           2.459   2                                                       ______________________________________                                          *Impurity peak                                                           

(c) The MgAPSO-47 compositions are generally characterized by the date of Table XXXI-B below:

                  TABLE XXXI-B                                                     ______________________________________                                         2Θ  d, (Å)      Relative Intensity                                   ______________________________________                                         9.5-9.65  9.33-9.17       vs                                                    12.85-13.05                                                                             6.89-6.79       vw-m                                                 16.0-16.2 5.54-5.46       w-m                                                   20.6-20.85                                                                              4.32-4.26       m-s                                                  24.75-25.3                                                                               3.598-3.526     vw-m                                                 30.55-30.95                                                                              2.925-2.889     w-m                                                  ______________________________________                                    

(d) the MgAPSO-47 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXXII-B below:

                  TABLE XXXII-B                                                    ______________________________________                                         2Θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                          9.5-9.65      9.33-9.17 100                                                   12.85-13.05    6.89-6.79  7-20                                                 13.9-14.2      6.36-6.25 3-7                                                   16.0-16.2      5.54-5.46 14-41                                                 17.65-18.0     5.03-4.92  4-11                                                 19.0-19.3      4.67-4.60 2-3                                                    20.6-20.85    4.32-4.26 33-89                                                 21.9-22.3      4.06-3.98 2-7                                                   23.0-23.3      3.866-3.819                                                                               3-11                                                 24.75-25.3     3.598-3.526                                                                               8-22                                                 25.85-26.2     3.444-3.400                                                                               7-18                                                 27.6-28.0      3.229-3.188                                                                              2-7                                                   27.95-28.5     3.190-3.132                                                                              1-4                                                    29.5-29.95    3.030-3.983                                                                              2-5                                                   30.55-30.95    2.925-2.889                                                                              13-36                                                 30.9-31.4      2.891-2.849                                                                              sh                                                    31.4-31.5      2.849-2.837                                                                              0-3                                                   32.4           2.763     0-1                                                    33.25         2.695     0-3                                                   34.4-34.8      2.606-2.575                                                                              3-7                                                   34.95          2.567     0-1                                                    35.8-36.55    2.510-2.459                                                                              1-4                                                   38.5           2.338     0-2                                                    39.1-39.65    2.305-2.273                                                                              0-4                                                   39.6-39.7      2.275-2.270                                                                              0-4                                                   42.5-42.8      2.126-2.115                                                                              0-3                                                   43.3-43.8      2.091-2.067                                                                              0-2                                                   47.6-47.7      1.911-1.907                                                                              0-3                                                   48.7-49.3      1.870-1.848                                                                              1-7                                                   50.4-51.1      1.810-1.787                                                                              1-5                                                   51.7           1.768     0-1                                                    52.45         1.745     0-1                                                   53.3           1.719     0-2                                                   54.1           1.695     0-1                                                   54.7           1.681     0-1                                                   55.9           1.645     0-2                                                   ______________________________________                                    

EXAMPLE 122B

In order to demonstrate the catalytic activity of the MgAPSO compositions, calcined samples of MgAPSO products were tested for catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test MgAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The MgAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the MgAPSO compositions. The k_(A) value (cm³ /g min) obtained for the MgAPSO compositions are set forth, below, in Table XXX-B:

                  TABLE XXX-B                                                      ______________________________________                                                     Prepared in                                                        MgAPSO      Example No.                                                                               Rate Constant (k.sub.Å)*                            ______________________________________                                         MgAPSO-35   80B        2.6                                                     MgAPSO-34   63B        4.1                                                     MgAPSO-35   82B        0.9                                                     MgAPSO-36    5B        18.0                                                    MgAPSO-46   44B        7.3                                                     MgAPSO-47   104B       1.7                                                     ______________________________________                                          *Prior to activation of the MgAPSO samples of the following examples such      were calcined as follows:                                                      (a) Example 80B: calcined in air at 600° for 2.25 hours;                (b) Example 63B: calcined in air at 550° C. for 2 hours;                (c) Example 82B: calcined in nitrogen at 425° C. for 2 hours;           (d) Example 5B: calcined in air at 500° C. for 2 hours and then at      600° C. for 2 hours;                                                    (e) Example 44B: calcined in nitrogen at 500° C. for 1.75 hours;        and                                                                            (f) Example 104B: calcined in air at 500° C. for 1.75 hours.      

IRON-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES

Molecular sieves containing iron, aluminum phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

In the following examples the FeAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isopropoxide, Al(OCH(CH₃)₂)₃ ;

(b) LUDOX-LS: LUDOX-LS is the trademark of Du Pont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: trademark for hydrated aluminum oxide containing about 75 wt. % Al₂ O₃ (pseudo-boehmite phase) and about 25 wt. percent water.

(c) Fe(Ac)₂ : Iron (II) acetate;

(d) FeSO₄ : Iron (II) sulfate hexahydrate;

(e) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;

(h) Pr₂ NH: di-n-propylamine ((C₃ H₇)₂ NH);

(i) Pr₃ N: tri-n-propylamine ((C₃ H₇)₃ N);

(j) Quin: Quinuclidine (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide (C₇ H₁₃ NCH₃ OH);

(l) TMAOH: tetramethylammonium hydroxide pentahydrate; and

(m) C-hex: cyclohexylamine.

EXAMPLES 1C to 16C

(a) Examples 1C to 8C were carried out to demonstrate the preparation of FeAPSO-34 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum isopropoxide in a blender followed by slowly adding the H₃ PO₄ solution with mixing. A solution/dispersion of iron acetate in water was added and then the LUDOX-LS was added. The organic templating agent was then added to this mixture, or in some cases one-half of this mixture, and the mixture blended to form a homogeneous mixture. The number of moles of each component in the reaction mixture was as follows:

    ______________________________________                                                Component      Moles                                                    ______________________________________                                                Al.sub.2 O.sub.3                                                                              0.9                                                             P.sub.2 O.sub.5                                                                               0.9                                                             SiO.sub.2      0.2**                                                           FeO*           0.2                                                             TEAOH          1.0                                                             H.sub.2 O      50                                                       ______________________________________                                          *Iron (II) acetate reported as Iron (II) oxide.                                **SiO.sub.2 was 0.6 in examples 5C to 8C                                 

Each reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at a temperature (see Table I-C), time (see Table I-C) and at the autogeneous pressure. The solid reaction product was recovered by filtration, washed with water and dried at room temperature. The products were analyzed and the observed FeAPSO products reported in Table I-C.

(b) Examples 9C to 16C were carried out to demonstrate the preparation of FeAPSO-11 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum iso-propoxide in a blender followed by addition of a solution/dispersion of Iron (II) acetate. H₃ PO₄ was added to this mixture and the resulting mixture blended to form a homogeneous mixture. LUDOX-LS was added to this mixture except that in examples 13C to 16C the LUDOX-LS was added with the H₃ PO₄. The resulting mixtures were blended until a homogeneous mixture was observed. Organic templating agent was added to each mixture and the resulting mixtures placed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated, washed and the product recovered as in part (a) of this example. The products were analyzed and the observed FeAPSO products reported in Table I-C. The number of moles of each component in the reaction mixture was as follows:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.9                                                                    P.sub.2 O.sub.5                                                                        0.9                                                                    SiO.sub.2                                                                              0.2                                                                    FeO*    0.2                                                                    Template                                                                               1.0                                                                    H.sub.2 O                                                                              50                                                              ______________________________________                                          *Iron (II) acetate reported as Iron (II) oxide.                          

(c) Two reaction mixtures, designated Examples AC and BC in Table I-C, did not show FeAPSO products when analyzed by X-ray. Examples AC and BC followed the same procedure employed for Examples 5C and 6C.

                  TABLE I-C                                                        ______________________________________                                                                             FeAPSO                                     Example                                                                               Template Temp (°C.)                                                                          Time (hr.)                                                                             Product.sup.1                              ______________________________________                                          1C    TEAOH    150          64     FeAPSO-34;                                                                     FeAPSO-5                                    2C    TEAOH    150         158     FeAPSO-34;                                                                     FeAPSO-5                                    3C    TEAOH    200          64     FeAPSO-34;                                                                     FeAPSO-5                                    4C    TEAOH    200         158     FeAPSO-34;                                                                     FeAPSO-5                                    5C    TEAOH    150          40     FeAPSO-34;                                                                     FeAPSO-5                                    6C    TEAOH    150         161     FeAPSO-34;                                                                     FeAPSO-5                                    7C    Pr.sub.2 NH  .sup.                                                                      150          50     FeAPSO-11                                   8C    Pr.sub.2 NH  .sup.                                                                      150         168     FeAPSO-11                                   9C    Pr.sub.2 NH  .sup.                                                                      200          50     FeAPSO-11                                  10C    Pr.sub.2 NH  .sup.                                                                      200         168     FeAPSO-11                                  11C    Pr.sub.3 N                                                                              150          50     FeAPSO-5                                   12C    Pr.sub.3 N                                                                              150         168     FeAPSO-5                                   13C    Pr.sub.3 N                                                                              200          50     FeAPSO-5                                   14C    Pr.sub.3 N                                                                              200         168     FeAPSO-5                                    AC    TEAOH    100          40     --                                          BC    TEAOH    100         161     --                                         ______________________________________                                          .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the major species observed. A "--" indicates no FeAPSO product       was present as determined by Xray analysis.                              

EXAMPLES 15C to 19C

Examples 15C to 19C were carried out according to the general preparative procedure employed for examples 7C to 14C with examples 15C to 18C following the procedure employed for examples 7C to 10C and example 19C following the procedure followed for examples 11C to 14C. The reactive source of iron was Iron (II) sulfate instead of Iron (II) acetate. The temperature and time for the crystallization (digestion) procedure are set forth in Table II-C.

The number of moles of each component in the reaction mixtures for examples 15C to 18C was as follows:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.9                                                                    P.sub.2 O.sub.5                                                                        0.9                                                                    SiO.sub.2                                                                              0.6                                                                    FeO*    0.2                                                                    Pr.sub.3 N                                                                             1.5                                                                    H.sub.2 O                                                                              50                                                              ______________________________________                                          *Iron (II) sulfate reported as Iron (II) oxide.                          

The number of moles of each component in the reaction mixture of example 19C was as follows:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.9                                                                    P.sub.2 O.sub.5                                                                        0.9                                                                    SiO.sub.2                                                                              0.2                                                                    FeO*    0.2                                                                    Pr.sub.3 N                                                                             1.0                                                                    H.sub.2 O                                                                              50                                                              ______________________________________                                          *Iron (II) sulfate reported as Iron (II) oxide.                          

The products were subjected to analysis by x-ray and the observed FeAPSO products reported in Table II-C.

                  TABLE II-C                                                       ______________________________________                                                                              FeAPSO                                    Example                                                                               Template Temp (°C.)                                                                          Time (hr.)                                                                              Product.sup.1                             ______________________________________                                         15C    Pr.sub.3 N                                                                              150          48      FeAPSO-5                                  16C    Pr.sub.3 N                                                                              150         160      FeAPSO-5                                  17C    Pr.sub.3 N                                                                              200          48      FeAPSO-5                                  18C    Pr.sub.3 N                                                                              200         160      FeAPSO-5                                  19C    Pr.sub.3 N                                                                              200          72      FeAPSO-5                                  ______________________________________                                          .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the major species observed.                                    

EXAMPLES 20C-27C

Examples 20C-27C were carried out according to the general preparative procedure employed for examples 1C to 8C using the following number of moles of each component in the reaction mixture:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.9                                                                    P.sub.2 O.sub.5                                                                        0.9                                                                    SiO.sub.2 *                                                                            0.2, 0.6                                                               FeO**   0.2                                                                    Template                                                                               1.0                                                                    H.sub.2 O                                                                              50                                                              ______________________________________                                          *0.2 moles in examples 20C to 23C and 0.6 moles in examples 24C to 27C         **Iron (II) acetate reported as Iron (II) oxide.                         

The temperature and time for the crystallization procedure and the observed FeAPSO products are reported in Table III-C.

                  TABLE III-C                                                      ______________________________________                                                                             FeAPSO                                     Example                                                                               Template Temp (°C.)                                                                          Time (hr.)                                                                             Product.sup.1                              ______________________________________                                         20C    Quin     150          64     FeAPSO-16                                  21C    Quin     150         158     FeAPSO-16;                                                                     FeAPSO-35                                  22C    Quin     200          64     FeAPSO-16;                                                                     FeAPSO-35                                  23C    Quin     200         158     FeAPSO-16;                                                                     FeAPSO-35                                  24C    MQuin    100          49     FeAPSO-16                                  25C    MQuin    100         161     FeAPSO-16                                  26C    MQuin    150          49     FeAPSO-16;                                                                     FeAPSO-35                                  27C    MQuin    150         161     FeAPSO-16;                                                                     FeAPSO-35                                  ______________________________________                                          .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two species were identified the first species        listed is the major species observed.                                    

EXAMPLES 28C AND 29C

Examples 28C and 29C were carried out according to the procedure of examples 13C to 16C, except that Iron (II) sulfate, was employed as the reactive iron source instead of Iron (II) acetate. The number of moles of each component in the reaction mixture for each example was as follows:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.8                                                                    P.sub.2 O.sub.5                                                                        1.0                                                                    SiO.sub.2                                                                              0.4                                                                    FeO*    0.4                                                                    Template                                                                               2.0                                                                    H.sub.2 O                                                                              83                                                              ______________________________________                                          *Iron (II) sulfate reported here as FeO                                  

Examples CC and DC followed the procedure for Examples 28C and 29C. X-ray analysis of the reaction products did not show FeAPSO products.

The temperature and time for the crystallization procedure and the observed FeAPSO products are reported in Table IV-C.

                  TABLE IV-C                                                       ______________________________________                                                                              FeAPSO                                    Example                                                                               Template Temp (°C.)                                                                          Time (hr.)                                                                              Product.sup.1                             ______________________________________                                         28C    TBAOH     200        49       FeAPSO-5                                  29C    TBAOH     200       161       FeAPSO-5                                  CC     TBAOH     150        49       --                                        DC     TBAOH     150       161       --                                        ______________________________________                                          .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the major species observed. A "--" indicates no FeAPSO product       was present as determined by Xray analysis.                              

EXAMPLES 30C TO 43C

Examples 30C to 43C were carried out according to the procedure employed for examples 1C to 8C except that in examples 30C and 31C the aluminum source was CATAPAL and in examples 33C to 36C and 43C a seed crystal of a topologically similar molecular sieve was employed. The number of moles of each component in the reaction mixture in examples 30C to 43C was:

    ______________________________________                                                Component                                                                              Moles                                                           ______________________________________                                                Al.sub.2 O.sub.3                                                                       0.9                                                                    P.sub.2 O.sub.5                                                                        0.9                                                                    SiO.sub.2                                                                               0.2**                                                                 FeO*    0.2                                                                    Template                                                                                1.0**                                                                 H.sub.2 O                                                                              50                                                              ______________________________________                                          *Iron (II) acetate reported here as FeO                                        **SiO.sub.2 was 0.6 in example 32C and was 2.0 moles of template in            examples 37C to 40C.                                                     

The template, temperature, time for the crystallization procedure and the observed FeAPSO products are reported in Table V-C.

                  TABLE V-C                                                        ______________________________________                                                                             FeAPSO                                     Example                                                                               Template Temp (°C.)                                                                          Time (hr.)                                                                             Product.sup.1                              ______________________________________                                         30C    TMAOH    150          42     FeAPSO-20                                  31C    TMAOH    150         132     FeAPSO-20                                  32C    C-hex  .sup.                                                                            220         114     FeAPSO-5;                                                                      FeAPSO-44                                  33C    Pr.sub.2 NH   .sup.                                                                     150          47     FeAPSO-31                                  34C    Pr.sub.2 NH   .sup.                                                                     150         182     FeAPSO-31                                  35C    Pr.sub.2 NH   .sup.                                                                     200          47     FeAPSO-31                                  36C    Pr.sub.2 NH   .sup.                                                                     200         158     FeAPSO-31                                  37C    Pr.sub.2 NH   .sup.                                                                     150         182     FeAPSO-46                                  38C    Pr.sub.2 NH   .sup.                                                                     150         182     FeAPSO-46                                  39C    Pr.sub.2 NH   .sup.                                                                     150          47     FeAPSO-5;                                                                      FeAPSO-34                                  40C    Pr.sub.2 NH   .sup.                                                                     200         158     FeAPSO-11;                                                                     FeAPSO-31                                  41C    Pr.sub.2 N                                                                              150          42     FeAPSO-5                                   42C    Pr.sub.2 N                                                                              150         132     FeAPSO-5                                   43C    Pr.sub.2 N                                                                              150          42     FeAPSO-5                                   EC     Pr.sub.2 NH   .sup.                                                                     150          47     --                                         ______________________________________                                          .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the major species observed. A "--" indicates no FeAPSO product       was present as determined by Xray analysis.                              

EXAMPLE 44C

(a) Samples of FeAPSO products were calcined at 600° C. in air for 2 hours to remove at least part of the organic templating agent, except that FeAPSO-5 and FeAPSO-11 were calcined for 2.25 hours. The example in which the FeAPSO was prepared is indicated in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the FeAPSO compositions are set forth hereinafter.

(b) FeAPSO-5 (example 12C):

    ______________________________________                                                  Kinetic    Pressure  Temp    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2  3.46       100       -183     9.7                                     O.sub.2  3.46       734       -183    11.6                                     neopentane                                                                              6.2        100       24.5     3.8                                     cyclohexane                                                                             6.0         59       23.7     5.7                                     H.sub.2 O                                                                               2.65          4.6    23.9    10.7                                     H.sub.2 O                                                                               2.65         20.0    23.6    19.2                                     ______________________________________                                    

The above data demonstrate that the pore size of the calcined product is greater than 6.2 Å.

(c) FeAPSO-11 (example 10C):

    ______________________________________                                                  Kinetic    Pressure  Temp    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2  3.46       100       -183    7.6                                      O.sub.2  3.46       734       -183    9.2                                      neopentane                                                                              6.2        100       24.5    0.2                                      cyclohexane                                                                             6.0         59       23.7    4.2                                      H.sub.2 O                                                                               2.65          4.6    23.9    10.8                                     H.sub.2 O                                                                               2.65         20.0    23.6    16.7                                     ______________________________________                                    

The above data demonstrate that the pore size of the calcined product is about 6.0 Å.

(d) FeAPSO-20 (example 31C):

    ______________________________________                                                  Kinetic    Pressure  Temp    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2  3.46        99       -183     1.5                                     O.sub.2  3.46       749       -183     8.5                                     H.sub.2 O                                                                               2.65          4.6    23.2    22.7                                     H.sub.2 O                                                                               2.65         16.8    23.5    30.0                                     ______________________________________                                    

The above data demonstrates that the pore size of the calcined product is about 3.0 Å.

(e) FeAPSO-31 (example 34C):

    ______________________________________                                                  Kinetic    Pressure  Temp    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2  3.46        99       -183    6.8                                      O.sub.2  3.46       749       -183    11.6                                     neopentane                                                                              6.2        100       23.4    3.6                                      cyclohexane                                                                             6.0         57       23.4    6.9                                      H.sub.2 O                                                                               2.65          4.6    23.2    6.5                                      H.sub.2 O                                                                               2.65         16.8    23.5    21.3                                     ______________________________________                                    

The above data demonstrates that the pore size of the calcined product is greater than about 6.2 Å.

(f) FeAPSO-46 (example 38C):

    ______________________________________                                                  Kinetic    Pressure  Temp    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2  3.46       100       -183    2.6                                      O.sub.2  3.46       749       -183    11.7                                     neopentane                                                                              6.2        100       23.4    1.1                                      cyclohexane                                                                             6.0         57       23.4    6.4                                      H.sub.2 O                                                                               2.65          4.6    23.2    7.2                                      H.sub.2 O                                                                               2.65         16.8    23.5    13.0                                     ______________________________________                                    

The above data demonstrates that the pore size of the calcined product is greater than about 6.2 Å.

EXAMPLE 45C

Samples of FeAPSO products were subjected to chemical analysis as follows:

(a) The chemical analysis for FeAPSO-5 (example 12C) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.2                                                             P.sub.2 O.sub.5                                                                              45.4                                                             FeO            4.7                                                             SiO.sub.2      1.9                                                             Carbon         4.9                                                             LOI*          14.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.14R:0.21 FeO; 1.0 Al₂ O₃ :1.01 P₂ O₅ :0.10 SiO₂ ; and a formula (anhydrous basis) of:

    0.03R(Fe.sub.0.05 Al.sub.0.46 P.sub.0.47 Si.sub.0.02)O.sub.2

(b) The chemical analysis of FeAPSO-11 (example 10C) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             33.2                                                             P.sub.2 O.sub.5                                                                              48.8                                                             FeO           4.5                                                              SiO.sub.2     2.4                                                              Carbon        5.1                                                              LOI*          9.8                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.22R:0.19FeO; 1.0 Al₂ O₃ ; 1.06 P₂ O₅ ; 0.08 SiO₂ ; and a formula (anhydrous basis) of: 0.05(Fe₀.04 Al₀.45 P₀.48 Si₀.03)O₂

(c) The chemical analysis of FeAPSO-20 (example 31C) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             29.1                                                             P.sub.2 O.sub.5                                                                              42.0                                                             FeO            4.8                                                             SiO.sub.2      2.5                                                             Carbon         7.6                                                             LOI*          19.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.55R:0.23FeO; 1.0 Al₂ O₃ ; 1.04 P₂ O₅ ; 0.15 SiO₂ ; and a formula (anhydrous basis) of: 0.12(Fe₀.05 Al₀.45 P₀.47 Si₀.03)O₂

(d) The chemical analysis of FeAPSO-31 (example 34C) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             34.7                                                             P.sub.2 O.sub.5                                                                              45.3                                                             FeO            4.2                                                             SiO.sub.2      1.6                                                             Carbon         3.4                                                             LOI*          12.9                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.14R:0.17FeO; 1.0 Al₂ O₃ ; 0.94 P₂ O₅ ; 0.08 SiO₂ ; and a formula (anhydrous basis) of: 0.03(Fe₀.04 Al₀.49 P₀.45 Si₀.02)O₂

EXAMPLE 46C

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals of FeAPSO products of the hereinafter designated examples. Analysis of crystals having a morphology characteristic of FeAPSO-5, FeAPSO-11, FeAPSO-20, FeAPSO-31, FeAPSO-34 and FeAPSO-46 gave the following analysis based on relative peak heights:

    ______________________________________                                                          Average of Spot Probes                                        ______________________________________                                         (a) FeAPSO-5 (example 12C):                                                    Fe                 0.02                                                        Al                 0.44                                                        P                  0.52                                                        Si                 0.02                                                        (b) FeAPSO-11 (example 10C):                                                   Fe                 0.03                                                        Al                 0.42                                                        P                  0.52                                                        Si                 0.03                                                        (c) FeAPSO-20 (example 31C):                                                   Fe                 0.04                                                        Al                 0.42                                                        P                  0.49                                                        Si                 0.05                                                        (d) FeAPSO-31 (example 34C):                                                   Fe                 0.01                                                        Al                 0.44                                                        P                  0.48                                                        Si                 0.06                                                        (e) FeAPSO-34 (example 3C):                                                    Fe                 0.04                                                        Al                 0.43                                                        P                  0.45                                                        Si                 0.07                                                        (f) FeAPSO-46 (example 38C):                                                   Fe                 0.05                                                        Al                 0.40                                                        P                  0.43                                                        Si                 0.12                                                        ______________________________________                                    

EXAMPLE 47C

(a) FeAPSO-5, as prepared in example 12C, was subjected to x-ray analysis. FeAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.4           11.95   100                                                      8.0*          11.05   4                                                        12.6*         7.03    13                                                       13.0          6.81    7                                                        14.95         5.93    15                                                       16.0*         5.54    <1                                                       16.5*         5.37    1                                                        17.1*         5.19    1                                                        18.4*         4.82    <1                                                       19.8          4.48    33                                                       20.3*         4.37    5                                                        21.1          4.21    27                                                       22.0*         4.04    sh                                                       22.4          3.969   38                                                       22.6*         3.934   sh                                                       24.7          3.604   2                                                        25.1*         3.548   1                                                        25.9          3.440   15                                                       27.2*         3.278   1                                                        28.0*         3.187   2                                                        28.4*         3.143   1                                                        29.0          3.079   6                                                        30.0          2.979   19                                                       31.8*         2.814   3                                                        33.7          2.660   2                                                        34.5          2.600   9                                                        35.2*         2.550   1                                                        37.0          2.564   1                                                        37.8          2.380   4                                                        41.6          2.171   1                                                        42.3          2.137   2                                                        42.9          2.108   1                                                        43.6          2.076   1                                                        45.0          2.015   1                                                        45.7*         1.985   1                                                        47.7          1.907   3                                                        51.5          1.774   1                                                        55.6          1.653   1                                                        ______________________________________                                          *peak contains impurity                                                  

(b) A portion of the as-synthesized FeAPSO-5 of part (a) was calcined in air at a temperature beginning at 500° C. and ending at 600° C. over a period of 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.4           11.95   100                                                      7.9*          11.19   sh                                                       8.45*         10.46   35                                                       12.85         6.89    18                                                       14.8          5.99    8                                                        15.5*         5.72    13                                                       16.4*         5.40    2                                                        17.0*         5.22    5                                                        19.75         4.50    31                                                       20.2*         4.40    14                                                       21.1          4.21    33                                                       21.4*         4.15    sh                                                       22.0*         4.04    sh                                                       22.45         3.960   83                                                       23.8*         3.739   1                                                        24.8          3.59    2                                                        25.1*         3.548   2                                                        25.95         3.434   31                                                       27.0*         3.302   2                                                        27.9*         3.198   3                                                        29.05         3.074   14                                                       30.05         2.974   22                                                       31.5*         2.840   29                                                       31.65         2.827   5                                                        34.55         2.596   15                                                       35.0*         2.564   3                                                        36.1*         2.488   1                                                        37.0          2.430   4                                                        37.8          2.380   8                                                        38.2*         2.356   2                                                        39.2*         2.298   2                                                        40.2*         2.151   2                                                        42.3          2.137   2                                                        43.0          2.103   1                                                        43.8          2.067   2                                                        45.2          2.006   2                                                        46.6*         1.949   2                                                        47.7          1.907   4                                                        51.6          1.771   4                                                        55.6          1.653   2                                                        ______________________________________                                          *peak contains impurity                                                  

(c) The FeAPSO-5 compositions are generally characterized by the data of Table VI-C below:

                  TABLE VI-C                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.3-7.5      12.11-11.79                                                                              m-vs                                                     14.8-14.95  5.99-5.93 w-m                                                     19.6-19.8    4.53-4.48 m                                                       21.0-21.2    4.23-4.19 m                                                       22.35-22.5   3.98-3.95 m-vs                                                     25.8-25.95  3.453-3.434                                                                              w-m                                                     ______________________________________                                    

(d) The FeAPSO-5 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VII-C, below:

                  TABLE VII-C                                                      ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.3-7.5      12.11-11.79                                                                               55-100                                                 12.8-13.0    6.92-6.81  7-18                                                    14.8-14.95  5.99-5.93 17-27                                                   19.6-19.8    4.53-4.48 24-60                                                   21.0-21.2    4.23-4.19 27-53                                                   22.35-22.5   3.98-3.95  38-100                                                  24.7-24.85  3.604-3.583                                                                              0-6                                                      25.8-25.95  3.453-3.434                                                                              15-68                                                   28.85-29.05  3.095-3.074                                                                               6-24                                                    29.8-30.05  2.998-2.974                                                                               9-27                                                   33.45-33.7   2.679-2.660                                                                               2-10                                                    34.4-34.55  2.607-2.596                                                                               8-17                                                   36.9-37.0    2.436-2.564                                                                              1-7                                                     37.65-37.9   2.389-2.374                                                                               4-13                                                   41.4-41.6    2.181-2.171                                                                              0-4                                                     42.1-42.3    2.146-2.137                                                                              0-4                                                     42.6-43.1    2.122-2.099                                                                              0-4                                                     43.5-43.8    2.080-2.067                                                                              0-4                                                     44.9-45.2    2.019-2.006                                                                              0-7                                                     47.6-47.7    1.910-1.907                                                                              0-5                                                     51.3-51.6    1.781-1.771                                                                              0-4                                                     55.4-55.6    1.658-1.653                                                                              1-6                                                     ______________________________________                                    

EXAMPLE 48C

(a) FeAPSO-11, as prepared in example 10C, was subjected to x-ray analysis. FeAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.1           10.92   31                                                       9.45          9.36    47                                                       13.15         6.73    15                                                       15.7          5.64    34                                                       16.2          5.47     5                                                       19.0          4.67     6                                                       20.3          4.37    43                                                       21.0          4.23    100                                                      22.1          4.022   62                                                       22.5*         3.952   sh                                                       22.65         3.926   61                                                       23.1          3.850   86                                                       24.7          3.604   10                                                       26.4          3.376   25                                                       28.2**        3.164   sh                                                       28.6          3.121   17                                                       29.0          3.079   sh                                                       29.5          3.028    7                                                       31.5          2.840    9                                                       32.7          2.755   19                                                       33.6**        2.667    2                                                       34.1          2.629    9                                                       36.3          2.415    6                                                       37.7          2.386   14                                                       39.2          2.298    5                                                       42.9          2.108    5                                                       44.7          2.027    6                                                       50.6          1.804    5                                                       54.7          1.678    5                                                       55.5          1.656    3                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized FeAPSO-11 of part (a) was calcined in air at 600° C. for about 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.05          10.98   60                                                       9.5           9.31    72                                                       12.9**        6.86    sh                                                       13.1          6.76    20                                                       13.7**        6.46     3                                                       14.7**        6.03     3                                                       15.9          5.57    55                                                       16.1          5.51    sh                                                       17.6**        5.04     3                                                       19.9**        4.46    sh                                                       20.3          4.37    28                                                       21.3          4.17    100                                                      21.9*         4.06    sh                                                       22.4          3.969   88                                                       23.0*         3.867   sh                                                       23.4          3.802   70                                                       24.0**        3.708    3                                                       24.4**        3.648    5                                                       25.0*         3.562    4                                                       25.8*         3.453    7                                                       26.5          3.363   20                                                       27.7**        3.220    5                                                       29.0          3.079   sh                                                       29.6          3.018   20                                                       30.4*         2.940    7                                                       31.8          2.814   10                                                       32.7          2.739   18                                                       34.1          2.629    5                                                       34.5**        2.600    4                                                       35.6*         2.522    4                                                       36.2          2.481    4                                                       38.0          2.368   10                                                       43.3          2.090    3                                                       44.8          2.023    5                                                       49.0*         1.859    3                                                       49.6*         1.838    3                                                       54.6          1.681    3                                                       55.7*         1.650    3                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The FeAPSO-11 compositions are generally characterized by the data of Table VIII-C below:

                  TABLE VIII-C                                                     ______________________________________                                         2θ  d, (Å)     Relative Intensity                                    ______________________________________                                         8.05-8.1  10.98-10.92    m-s                                                   9.4-9.5   9.41-9.31      m                                                     21.0-21.3 4.23-4.17      vs                                                    22.1-22.4 4.022-3.969    m-s                                                   22.65-23.1                                                                               3.926-3.850    vw-m                                                  23.1-23.4 3.850-3.802    m-s                                                   ______________________________________                                    

(d) The FeAPSO-11 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table IX-C, below:

                  TABLE IX-C                                                       ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         8.05-8.1       10.98-10.92                                                                              30-80                                                 9.4-9.5        9.41-9.31 47-78                                                 13.05-13.2     6.78-6.71 13-24                                                 15.7-15.9      5.64-5.57 33-54                                                 16.15-16.3     5.49-5.44 0-6                                                    18.9-19.05    4.70-4.66 0-6                                                   20.2-20.4      4.40-4.35 30-43                                                 21.0-21.3      4.23-4.17 100                                                   21.9           4.06      sh                                                    22.1-22.4      4.022-3.969                                                                              54-86                                                 22.5-22.6      3.952-3.934                                                                              sh                                                    22.65-23.1     3.926-3.850                                                                              sh-61                                                 23.1-23.4      3.850-3.802                                                                              48-86                                                 24.4-24.5      3.648-3.633                                                                              sh-6                                                  24.7-24.9      3.604-3.576                                                                               0-10                                                 26.4-26.5      3.376-3.363                                                                              15-25                                                 28.6-28.8      3.121-3.100                                                                              17-19                                                 28.9-29.0      3.079-3.089                                                                              sh                                                    29.5-29.6      3.028-3.018                                                                               7-21                                                 31.5-31.8      2.840-2.814                                                                               8-12                                                  32.7-32.85    2.755-2.726                                                                              13-19                                                  34.1-34.25    2.629-2.618                                                                              5-9                                                   36.2-36.5      2.481-2.462                                                                              5-7                                                   37.6-38.0      2.392-2.368                                                                               7-14                                                 39.2-39.4      2.298-2.287                                                                              2-5                                                   42.9-43.2      2.108-2.094                                                                              3-5                                                   44.7-44.9      2.027-2.019                                                                              3-6                                                   48.3-48.4      1.884-1.881                                                                              0-2                                                   50.5-50.9      1.807-1.794                                                                              0-5                                                   54.5-54.8      1.684-1.675                                                                              0-5                                                   55.4-55.6      1.658-1.653                                                                              0-3                                                   ______________________________________                                    

EXAMPLE 49C

(a) FeAPSO-16, as prepared in example 21C, was subjected to x-ray analysis. FeAPSO-16 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.6**         10.28   7                                                       10.9**         8.12    sh                                                      11.3           7.83    58                                                      13.2**         6.71    8                                                       15.8**         5.61    2                                                        17.25**       5.14    21                                                      17.7**         5.01    2                                                       18.65          4.76    40                                                      20.3**         4.37    sh                                                      20.7**         4.29    sh                                                      21.1**         4.21    sh                                                      21.85          4.07    100                                                     22.9           3.883   10                                                      23.6**         3.770   2                                                       25.0**         3.562   1                                                       25.8**         3.453   1                                                       26.5           3.363   22                                                      27.1**         3.290   sh                                                      28.6**         3.121   sh                                                      28.9           3.089   9                                                       29.7           3.008   24                                                      32.0**         2.797   10                                                      32.6           2.747   4                                                       34.6*          2.592   8                                                       35.6**         2.522   1                                                       37.85          2.377   8                                                       39.7           2.270   3                                                       44.3           2.045   2                                                       48.45*         1.879   7                                                       49.4**         1.845   2                                                       51.4**         1.778   1                                                       52.4           1.746   1                                                       54.8*          1.675   2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The FeAPSO-16 compositions are generally characterized by the data of Table X-C below:

                  TABLE X-C                                                        ______________________________________                                         2θ   d, (Å)     Relative Intensity                                   ______________________________________                                         11.3-11.4  7.83-7.76      m                                                    18.55-18.75                                                                               4.78-4.73      m                                                    21.85-22.0 4.07-4.04      vs                                                   26.45-26.6 3.370-3.351    w-m                                                  29.6-29.8  3.018-2.998    w-m                                                  ______________________________________                                    

(c) The FeAPSO-16 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XI-C, below:

                  TABLE XI-C                                                       ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         11.3-11.4      7.83-7.76 38-63                                                 18.55-18.75    4.78-4.73 31-63                                                 21.85-22.0     4.07-4.04 100                                                   22.9           3.883     sh-10                                                 26.45-26.6     3.370-3.351                                                                              18-26                                                 28.9-29.0      3.089-3.079                                                                               0-13                                                 29.6-29.8      3.018-2.998                                                                              17-30                                                 32.4-32.8      2.763-2.730                                                                               0-13                                                 34.5-34.6      2.600-2.592                                                                               0-10                                                 37.65-37.9     2.389-2.374                                                                               0-10                                                 39.5-39.7      2.281-2.270                                                                              0-6                                                   44.1-44.5      2.054-2.036                                                                              0-6                                                   48.2-48.5      1.888-1.877                                                                              0-8                                                   52.0-52.4      1.759-1.746                                                                              0-3                                                   54.4-54.8      1.687-1.675                                                                              0-3                                                   ______________________________________                                    

EXAMPLE 50C

(a) FeAPSO-20, as prepared to in example 31C, was subjected to x-ray analysis. FeAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         14.0           6.32    59                                                       19.85         4.47    47                                                       22.25         3.998   4                                                        24.35         3.654   100                                                     28.2           3.164   16                                                      31.6           2.831   12                                                      34.7           2.584   16                                                      37.6           2.394   2                                                       40.3           2.240   4                                                        42.85         2.110   5                                                        47.65         1.909   4                                                       52.0           1.758   8                                                       ______________________________________                                    

(b) A portion of the as-synthesized FeAPSO-20 of part (a) was calcined in air heating the sample from 500° C. to 600° C. over a period of 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.05*         12.56   6                                                        7.5*          11.82   6                                                        14.05         6.31    100                                                      20.02         4.43    28                                                       22.6          3.935   6                                                        23.85*        3.733   5                                                        24.5          3.635   45                                                       28.4          3.143   11                                                       31.7          2.823   11                                                       34.8          2.578   9                                                        ______________________________________                                          *impurity peak                                                           

(c) The FeAPSO-20 compositions are generally characterized by the data of Table XII-C below:

                  TABLE VI-C                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         13.95-14.0   6.34-6.33 m-vs                                                    19.8-20.0    4.48-4.44 m                                                       24.3-24.5    3.663-3.633                                                                              m-vs                                                    28.15-28.4   3.169-3.143                                                                              w                                                       31.6-31.7    2.831-2.823                                                                              w                                                       34.7-34.8    2.585-2.578                                                                              w                                                       ______________________________________                                    

(d) The FeAPSO-20 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIII-C, below:

                  TABLE XIII-C                                                     ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         13.95-14.0     6.34-6.33  57-100                                               19.8-20.0      4.48-4.44 28-47                                                 22.25-22.6     3.998-3.935                                                                              3-6                                                   24.3-24.5      3.663-3.633                                                                               45-100                                               28.15-28.4     3.169-3.143                                                                              11-16                                                 31.6-31.7      2.831-2.823                                                                              11-12                                                 34.7-34.8      2.585-2.578                                                                               9-16                                                 37.6           2.392     2-3                                                   40.2-40.3      2.242-2.240                                                                              4                                                      42.7-42.85    2.114-2.110                                                                              5                                                     47.5-47.6      1.914-1.909                                                                              3-4                                                   52.0           1.759     8                                                     ______________________________________                                    

EXAMPLE 51C

(a) FeAPSO-31, as prepared in example 34C, was subjected to x-ray analysis. FeAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.5           10.41   64                                                        9.45*        9.35    5                                                       13.0           6.81    1                                                       14.6           6.07    1                                                       15.7           5.64    3                                                        17.05         5.20    6                                                       18.3           4.85    3                                                        20.25         4.39    49                                                       21.05*        4.22    9                                                        21.95         4.05    32                                                      22.6           3.936   100                                                     23.2           3.833   6                                                       25.1           3.546   4                                                        25.65         3.474   4                                                        26.45         3.372   2                                                       27.9           3.195   13                                                      28.7           3.110   1                                                       29.7           3.008   7                                                       31.7           2.821   20                                                      32.7           2.739   1                                                        35.15         2.555   9                                                       36.1           2.489   2                                                       37.2           2.418   2                                                        37.65         2.390   2                                                        38.15         2.358   3                                                       39.3           2.293   4                                                       39.6           2.275   3                                                       40.2           2.244   2                                                       45.2           2.006   2                                                        46.65         1.947   3                                                        48.65         1.871   2                                                        50.75         1.799   2                                                        51.65         1.770   4                                                       55.5           1.650   2                                                       ______________________________________                                          *Peak may contain impurity                                               

(b) A portion of the as-synthesized FeAPSO-31 of part (a) was calcined in air at 600° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.6           10.26   73                                                       9.8*          9.04    3                                                        12.95         6.83    1                                                       14.9           5.95    5                                                       16.2           5.46    4                                                       17.2           5.16    11                                                       18.45         4.80    4                                                       20.4           4.35    50                                                       22.15         4.016   44                                                       22.75         3.909   100                                                      23.45         3.795   3                                                       25.3           3.521   5                                                       25.8           3.449   9                                                       28.1           3.174   13                                                      29.9           2.990   12                                                       31.1**        2.876   2                                                       31.9           2.806   30                                                      32.7           2.739   2                                                       35.3           2.542   10                                                      36.3           2.475   5                                                        37.35         2.407   3                                                        37.85         2.378   2                                                        38.35         2.346   3                                                       39.5           2.282   4                                                        40.35         2.234   3                                                        44.15         2.052   2                                                        45.05*        2.013   2                                                       45.4           1.997   2                                                        46.85         1.940   5                                                        47.65         1.909   2                                                       48.9           1.863   3                                                       49.3           1.848   2                                                        50.95         1.793   2                                                       51.8           1.765   6                                                       55.6           1.653   3                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The FeAPSO-31 compositions are generally characterized by the data of Table XIV-C below:

                  TABLE XIV-C                                                      ______________________________________                                         2θ d, (Å)      Relative Intensity                                    ______________________________________                                         8.5-8.6  10.40-10.28     w-s                                                   20.2-20.4                                                                               4.40-4.35       m                                                     21.1-21.2                                                                               4.21-4.19       w                                                     22.0-22.1                                                                               4.040-4.022     m                                                     22.6-22.7                                                                               3.934-3.917     vs                                                    31.7-31.9                                                                               2.822-2.805     w-m                                                   ______________________________________                                    

(d) The FeAPSO-31 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XV-C below:

                  TABLE XV-C                                                       ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.5-8.6       10.40-10.28                                                                              10-88                                                  9.5-9.8       9.35-9.04  3-11                                                   9.9          8.92      0-3                                                    13.0-13.3     6.81-6.67 1-4                                                    14.6-14.9     6.07-5.95 0-5                                                    15.7-16.2     5.64-5.46 3-7                                                    17.0-17.2     5.20-5.17  5-11                                                  18.3-18.5     4.84-4.80 2-4                                                    20.2-20.4     4.40-4.35 36-50                                                  21.1-21.2     4.21-4.19  9-18                                                  22.0-22.1     4.040-4.022                                                                              26-44                                                  22.6-22.7     3.934-3.919                                                                              100                                                    23.2-23.4     3.833-3.795                                                                               3-12                                                  25.1-25.3     3.546-3.521                                                                              4-5                                                    25.6-25.8     3.474-3.449                                                                              3-9                                                    26.4-26.6     3.372-3.352                                                                              0-5                                                    27.4-27.5     3.258-3.248                                                                              2-4                                                    27.9-28.1     3.195-3.174                                                                              12-14                                                  28.3          3.152     0-3                                                    28.7-28.8     3.111-3.103                                                                              0-3                                                    29.7-29.9     3.008-2.990                                                                               6-12                                                  31.1          2.876     0-2                                                    31.7-31.9     2.822-2.805                                                                              19-30                                                  32.7-33.0     2.739-2.718                                                                               0-3                                                   35.1-35.3     2.555-2.542                                                                               9-10                                                  36.1-36.3     2.489-2.475                                                                              2-5                                                    37.3-37.4     2.418-2.407                                                                              0-3                                                    37.6-37.8     2.390-2.378                                                                              2-3                                                    38.1-38.4     2.365-2.346                                                                              2-3                                                    39.3-39.5     2.293-2.282                                                                              3- 4                                                   39.6-39.7     2.275-2.271                                                                              0-3                                                    40.2-40.3     2.244-2.239                                                                              0-3                                                    44.1          2.052     0-2                                                    44.9          2.020     0-2                                                    45.0-45.1     2.015-2.012                                                                              0-2                                                    45.2-45.4     2.006-1.997                                                                              2-3                                                    46.6-46.8     1.947-1.940                                                                              3-5                                                    47.5-47.6     1.914-1.909                                                                              0-2                                                    48.6-48.9     1.872-1.863                                                                              2-3                                                    49.1-49.3     1.854-1.848                                                                              0-3                                                    50.8-50.9     1.799-1.793                                                                              0-2                                                    51.6-51.8     1.771-1.765                                                                              0-4                                                    55.5-55.6     1.657-1.653                                                                              0-3                                                    ______________________________________                                    

EXAMPLE 52C

(a) FeAPSO-34, as prepared in example 3C, was subjected to x-ray analysis. FeAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.3*          12.1    5                                                        9.35          9.5     100                                                     12.7           7.0     10                                                      14.0           6.3     8                                                        14.8*         5.99    2                                                       15.9           5.57    32                                                      17.9           4.96    7                                                        19.6*         4.53    3 (sh)                                                  20.4           4.35    50                                                      22.3           3.99    6                                                       22.9           3.88    2                                                       25.1           3.548   10                                                      25.7           3.466   11                                                      27.5           3.243   2                                                       28.2           3.164   2                                                       29.4           3.038   2 (sh)                                                  30.4           2.940   19                                                      31.1           2.876   12                                                      34.4           2.607   4                                                       36.2           2.481   2                                                       39.5           2.281   2                                                       43.3           2.090   3                                                       47.5           1.914   2                                                       48.9           1.863   3                                                       51.0           1.791   2                                                       53.0           1.728   2                                                       54.5           1.684   1                                                       ______________________________________                                          *Impurity peak                                                           

(b) A portion of the as-synthesized FeAPSO-34 of part (a) was calcined in air at 600° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.5*          11.79   7                                                        9.6           9.21    100                                                     13.0           6.81    17                                                      16.2           5.47    9                                                       16.9           5.25    1                                                       18.0           4.93    5                                                       19.3           4.60    5                                                        19.9*         4.46    2                                                       20.9           4.25    17                                                       22.55         3.943   7                                                       23.4           3.802   2                                                       24.2           3.678   2                                                       25.1           3.548   5                                                       26.2           3.401   7                                                        27.2*         3.278   1                                                       28.2           3.164   2                                                       29.2           3.058   2                                                       31.0           2.885   16                                                      ______________________________________                                          *Impurity peak                                                           

(c) The FeAPSO-34 compositions are generally characterized by the data of Table XVI-C below:

                  TABLE XVI-C                                                      ______________________________________                                         2θ  d, (Å)     Relative Intensity                                    ______________________________________                                         9.35-9.7  9.46-9.12      vs                                                    12.7-13.0 6.97-9.81      w-m                                                   15.9-16.2 5.57-5.47      w-m                                                   20.4-20.9 4.35-4.25      w-s                                                   22.3-22.5 3.99-3.95      vw--s                                                 25.7-26.2 3.466-3.401    vw-m                                                  ______________________________________                                    

(d) The FeAPSO-34 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVII-C below:

                  TABLE XVII-C                                                     ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.35-9.7      9.46-9.12 100                                                    12.7-13.0     6.97-6.81 10-25                                                  13.9-14.1     6.37-6.28  2-11                                                  15.9-16.2     5.57-5.47  9-47                                                  17.6-18.0     5.04-4.93  5-16                                                  18.9-19.3     4.70-4.60 0-5                                                    20.4-20.9     4.35-4.25 17-89                                                  22.3-22.5     3.99-3.95  4-88                                                  22.9-23.4     3.88-3.52 2-8                                                    24.8-25.3     3.59-3.52  5-18                                                  25.7-26.2     3.466-3.401                                                                               7-32                                                  27.5-27.6     3.243-3.232                                                                              0-5                                                    28.0-28.4     3.187-3.143                                                                              1-3                                                    29.4-29.6     3.038-3.018                                                                              0-4 (sh)                                               30.4-30.6     2.940-2.922                                                                               0-28                                                  31.0-31.2     2.885-2.867                                                                              2 (sh)-17                                              32.4          2.763     0-1                                                    34.4-34.6     2.607-2.592                                                                               0-13                                                  35.9-36.3     2.501-2.475                                                                              0-3                                                    39.5-39.6     2.281-2.276                                                                              0-3                                                    43.3-43.4     2.090-2.085                                                                              0-4                                                    47.5-47.6     1.914-1.910                                                                              0-5                                                    48.6-49.1     1.873-1.855                                                                              0-7                                                    50.6-51.1     1.804-1.787                                                                              0-3                                                    53.0-53.2     1.728-1.722                                                                              0-3                                                    54.5-54.6     1.684-1.681                                                                              0-1                                                    ______________________________________                                    

EXAMPLE 53C

(a) FeAPSO-35, as prepared in example 27C, was subjected to x-ray analysis. FeAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          8.7           10.19   5                                                       11.0           8.03    sh                                                       11.4**        7.77    51                                                      13.5           6.57    9                                                       16.0           5.55    3                                                       17.4           5.09    28                                                      17.9           4.95    5                                                         18.65**      4.76    50                                                      21.0           4.22    15                                                      21.9           4.06    100                                                      22.9**        3.885   9                                                        23.45         3.793   8                                                       25.1           3.548   3                                                        26.5**        3.365   25                                                       27.15         3.285   7                                                       28.6           3.118   16                                                       28.9*         3.091   (sh)                                                     29.7**        3.010   27                                                      32.2           2.780   (sh)                                                     32.5**        2.754   13                                                      34.6           2.591   7                                                        37.8*         2.381   10                                                       44.1**        2.053   3                                                        48.25*        1.886   8                                                       51.6           1.774   1                                                         52.15**      1.754   2                                                        54.5**        1.684   3                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The FeAPSO-35 compositions are generally characterized by the data of Table XVIII-C below:

                  TABLE XVIII-C                                                    ______________________________________                                         2-         d, (Å)     Relative Intensity                                   ______________________________________                                         10.9-11.1  8.12-7.97      vw-m                                                 13.2-13.5  6.71-6.56      vw-w                                                 17.2-17.4  5.16-5.10      w-m                                                  21.85-22.0 4.07-4.04      vs                                                   23.2-23.8  3.834-3.739    vw-m                                                  32.0-32.25                                                                               2.797-2.776    vw-m                                                 ______________________________________                                    

(c) The FeAPSO-35 compositions are generally characterized by the x-ray powder diffraction pattern shown in Table XIX-C, below:

                  TABLE XIX-C                                                      ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         8.6-8.7        10.28-10.19                                                                              0-14                                                  10.9-11.1      8.12-7.97 sh-38                                                 13.2-13.5      6.71-6.56 7-19                                                  15.8-16.2      5.61-5.47 1-6                                                   17.2-17.4      5.16-5.10 11-41                                                 17.75-17.9     5.00-4.95 sh-8                                                   20.8-21.25    4.27-4.18 sh-15                                                 21.85-22.0      4.07-4.040                                                                              100                                                   23.2-23.8      3.834-3.739                                                                              0-20                                                  24.9-25.1      3.576-3.548                                                                              0-3                                                    26.9-27.15    3.314-3.285                                                                              0-15                                                   28.5-28.65    3.132-3.114                                                                              sh-16                                                 28.8-29.0      3.100-3.082                                                                              0-sh                                                   32.0-32.25    2.797-2.776                                                                              sh-24                                                 34.5-34.9      2.600-2.571                                                                              3-8                                                   37.7-38.1      2.386-2.362                                                                              6-10                                                  ______________________________________                                    

EXAMPLE 54C

(a) FeAPSO-44, as prepared in example 32C, was subjected to x-ray analysis. FeAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.5**         11.80   670                                                     9.5            9.29    94                                                      12.95*         6.83    70                                                       14.95**       5.92    132                                                     16.15          5.48    30                                                      17.4           5.10     7                                                      19.0           4.67     7                                                      19.8**         4.48    326                                                     21.0*          4.23    332                                                     21.8           4.07    34                                                       22.45**       3.963   631                                                     23.1           3.850    7                                                      24.5           3.635   100                                                     24.7**         3.604   40                                                      26.0*          3.425   193                                                      27.15**       3.283   30                                                      28.05*         3.180   19                                                       29.05**       3.075   110                                                     30.1*          2.966   137                                                     30.9           2.894   40                                                      33.0           2.714    7                                                       33.65**       2.664   37                                                      34.6**         2.591   105                                                     35.55          2.525   128                                                     37.0**         2.430   28                                                       37.65**       2.389   82                                                      42.3*          2.137   23                                                      42.55*         2.125   17                                                      43.7*          2.072   15                                                      45.1**         2.011   14                                                      47.75*         1.904   36                                                      51.6**         1.77    17                                                      52.0**         1.758   16                                                      55.8**         1.647   19                                                      ______________________________________                                          *peak might contain impurity                                                   **impurity peak                                                          

(b) The FeAPSO-44 compositions are generally characterized by the data of Table XX-C below:

                  TABLE XX-C                                                       ______________________________________                                         2θ                                                                               d, (Å)     Relative Intensity*                                     ______________________________________                                         9.5     9.31           m                                                       12.95   6.83           m                                                       16.15   5.49           vw                                                      21.0    4.23           vs                                                      24.5     3.631         m                                                       30.9     2.894         w                                                       ______________________________________                                          *peak intensities were low and may affect accuracy                       

(c) The FeAPSO-44 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXI-C below:

                  TABLE XXI-C                                                      ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io*                                        ______________________________________                                          9.5          9.31    28                                                        12.95        6.83    21                                                        16.15        5.49     9                                                       17.4          5.10     2                                                       19.0          4.67     2                                                       21.0          4.23    100                                                      21.8          4.07    10                                                       23.1          3.850    2                                                       24.5          3.635   30                                                       26.0          3.427   58                                                        28.05        3.180    6                                                       30.1          2.966   11                                                       30.9          2.894   12                                                       33.0          2.714    2                                                        35.55        2.525   39                                                       42.3          2.137    7                                                        42.55        2.125    5                                                       43.7          2.072    5                                                        47.75        1.904   11                                                       ______________________________________                                          *peak intensities were low and may effect accuracy                       

EXAMPLE 55C

(a) FeAPSO-46, as prepared in example 38C was subjected to x-ray analysis. FeAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         6.6            13.42   3                                                        7.75          11.38   100                                                      12.45         7.11    2                                                       13.2           6.70    2                                                       13.8           6.41    1                                                       15.0           5.91    1                                                        15.35         5.77    1                                                       16.7           5.31    2                                                       17.3           5.13    <1                                                      19.9           4.47    1                                                       20.6           4.31    3                                                        21.65         4.11    7                                                       22.9           3.885   4                                                       24.3           3.660   3                                                       25.2           3.534   <1                                                       26.95         3.307   3                                                        27.85         3.206   2                                                        28.35         3.147   1                                                        28.85         3.093   3                                                        29.95         2.985   1                                                       30.2           2.959   <1                                                       30.95         2.889   <1                                                       31.35         2.855   2                                                       31.8           2.814   <1                                                       33.05         2.711   1                                                       34.4           2.606   1                                                        36.05         2.490   3                                                       36.7           2.448   <1                                                      39.9           2.259   <1                                                       41.25         2.188   <1                                                      44.2           2.049   1                                                        47.85         1.902   1                                                       50.4           1.811   <1                                                      51.7           1.768   <1                                                      52.5           1.743   <1                                                      ______________________________________                                    

(b) A portion of the as-synthesized FeAPSO-46 of part (a) was calcined in air at 500° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          6.85          12.92   9                                                        8.0           11.04   100                                                     13.6           6.51    4                                                        15.35         5.76    3                                                       16.0           5.55    3                                                        17.15         5.17    3                                                       21.3           4.17    2                                                       22.2           4.006   2                                                        23.45         3.793   2                                                       24.9           3.575   2                                                       27.6           3.232   2                                                       32.0           2.797   2                                                       ______________________________________                                    

(c) The FeAPSO-46 compositions are generally characterized by the data of Table XXII-C below.

                  TABLE XXII-C                                                     ______________________________________                                         2θ  d, (Å)     Relative Intensity                                    ______________________________________                                         6.6-6.8   13.39-13.00    vw                                                    7.8-8.0   11.33-11.05    vs                                                    13.2-13.6 6.71-6.51      vw                                                    21.65-22.2                                                                               4.10-4.00      vw                                                     22.9-23.45                                                                              3.883-3.793    vw                                                    26.95-27.6                                                                               3.308-3.232    vw                                                    ______________________________________                                    

(d) The FeAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIII-C below:

                  TABLE XXIII-C                                                    ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         6.6-6.8       13.39-13.00                                                                              3-9                                                    7.8-8.0       11.33-11.05                                                                              100                                                    12.45-12.6    7.11-7.03 0-3                                                    13.2-13.6     6.71-6.51 2-4                                                    13.8-14.0     6.41-6.33 1-2                                                     15.0-15.35   5.91-5.76 1-3                                                    15.35-16.0    5.77-5.55 1-3                                                     16.7-17.15   5.31-5.17 2-3                                                    17.3          5.13      0-1                                                    19.9-20.5     4.47-4.43 1-2                                                    20.6-21.3     4.31-4.17 2-3                                                    21.65-22.2    4.10-4.00 2-8                                                     22.9-23.45   3.883-3.793                                                                              2-4                                                    24.3-24.9     3.659-3.575                                                                              2-3                                                    25.2          3.534     0-1                                                    26.95-27.6    3.308-3.232                                                                              2-4                                                    27.85-27.95   3.206-3.190                                                                              0-3                                                    28.35-28.55   3.147-3.125                                                                              0-2                                                    28.85-29.05   3.093-3.076                                                                              0-3                                                    29.95-30.1    2.985-2.968                                                                              0-1                                                    30.2          2.959     0-1                                                    30.95         2.889     0-1                                                    31.3-32.0     2.855-2.797                                                                               2                                                      31.8-32.05   2.814-2.792                                                                              0-1                                                    33.05         2.711     0-1                                                    34.4          2.608     0-1                                                    36.05-36.2    2.490-2.481                                                                              0-3                                                    36.7          2.448     0-1                                                    39.9          2.259     0-1                                                    41.25         2.188     0-1                                                     44.2-44.35   2.049-2.043                                                                              0-1                                                    47.8-48.0     1.902-1.895                                                                              0-1                                                    50.4          1.811     0-1                                                    51.7          1.768     0-1                                                    52.5          1.743     0-1                                                    ______________________________________                                    

EXAMPLE 56C

In order to demonstrate the catalytic activity of the FeAPSO compositions, calcined samples of FeAPSO products were tested for the catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the selected FeAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium and n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the FeAPSO compositions. The k_(A) value (cm³ /g min) obtained for the FeAPSO compositions are set forth, below, in Table XXIV-C:

                  TABLE XXIV-C                                                     ______________________________________                                         FeAPSO of                                                                      Example No:.sup.1                                                                              Rate Constant (k.sub.A)                                        ______________________________________                                         FeAPSO-5 (Ex. 12 C)                                                                            0.5                                                            FeAPSO-11 (Ex. 10 C)                                                                           0.7                                                            FeAPSO-31 (Ex. 34 C)                                                                           1.3                                                            FeAPSO-46 (Ex. 37 C)                                                                           0.9                                                            ______________________________________                                          .sup.1 FeAPSO were calcined as follows prior to being activated:               (a)FeAPSO-5: at 600° C. in air for 2 hours;                             (b)FeAPSO-11: at 600° C. in air for 2.25 hours;                         (c)FeAPSO-31: at 500° C. to 600° C. in air for 2 hours; and      (d)FeAPSO-46: heated from 100° C. to 600° C. in nitrogen         over a 2hour period.                                                     

MANGANESE-ALUMINUM-PHOSPHORUS-SILICON-OXIDE MOLECULAR SIEVES

Molecular sieves containing manganese, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents

In the following examples the MnAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) MnAc: Manganese acetate, Mn (C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol.

PREPARATIVE PROCEDURES

The following preparative examples were carried out by forming a starting reaction mixture by adding the H₃ PO₄ to one half of the quantity of water. This mixture was mixed and to this mixture the aluminum isopropoxide or CATAPAL was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using the manganese acetate and the remainder (about 50%) of the water. The two mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. (The pH of the mixture was measured and adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for a time or placed in lined screw top bottles for digestion at 100° C. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture with H₃ PO₄ and MnAc are given respectively in terms of P₂ O₅ and MnO content of the reaction mixture.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

EXAMPLES 1D TO 64D

MnAPSO molecular sieves were prepared according to the above identified procedure and the MnAPSO products determined by X-ray analysis. The results of examples 1D to 64D are set forth in Tables I-D to IV-D.

                  TABLE I-D                                                        ______________________________________                                                                             MnAPSO                                     Example.sup.1                                                                          Template Temp (°C.)                                                                        Time (days)                                                                             Product.sup.2                              ______________________________________                                          1D     TEAOH    150       4        MnAPSO-34;                                                                     MnAPSO-5                                    2D     TEAOH    150       11       MnAPSO-5;                                                                      MnAPSO-34                                   3D     TEAOH    200       4        MnAPSO-5;                                                                      MnAPSO-34                                   4D     TEAOH    200       11       MnAPSO-5;                                                                      MnAPSO-34                                   5D     TEAOH    100       2        --.sup.3                                    6D     TEAOH    100       7        MnAPSO-34                                   7D     TEAOH    150       2        MnAPSO-34;                                                                     MnAPSO-5                                    8D     TEAOH    150       7        MnAPSO-34;                                                                     MnAPSO-5                                    9D     TEAOH    200       2        MnAPSO-5;                                                                      MnAPSO-34                                  10D     TEAOH    200       7        MnAPSO-5;                                                                      MnAPSO-34                                  11D     TEAOH    100       14       MnAPSO-34                                  12D     TEAOH    150       14       MnAPSO-34;                                                                     MnAPSO-5                                   13D     TEAOH    200       14       MnAPSO-5;                                                                      MnAPSO-34                                  ______________________________________                                          .sup.1 The reaction mixture comprised: 1.0 TEAOH: 0.2 MnO: 0.9 Al.sub.2        O.sub.3 : 0.9 P.sub.2 O.sub.5 : rSiO.sub.2 : 50 H.sub.2 O where "r" was        0.2 for examples 1D to 4D and was 0.6 for examples 5D to 13D.                  .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the predominant species observed.                                    .sup.3 No MnAPSO products were observed by xray analysis.                

                  TABLE II-D                                                       ______________________________________                                                                             MnAPSO                                     Example.sup.1                                                                         Template Temp (°C.)                                                                         Time (days)                                                                             Product.sup.2                              ______________________________________                                         14D    Quin     150        4        MnAPSO-16;                                                                     MnAPSO-35                                  15D    Quin     150        11       MnAPSO-16;                                                                     MnAPSO-35                                  16D    Quin     200        4        MnAPSO-16;                                                                     MnAPSO-35                                  17D    Quin     200        11       MnAPSO-16;                                                                     MnAPSO-35                                  18D    Quin     100        4        MnAPSO-35                                  19D    Quin     100        11       MnAPSO-35                                  20D    MQuin    150        2        MnAPSO-35;                                                                     MnAPSO-16                                  21D    MQuin    150        7        MnAPSO-35                                  22D    MQuin    200        2        MnAPSO-35                                  23D    MQuin    200        7        MnAPSO-35                                  24D    Pr.sub.2 NH                                                                             150        4        MnAPSO-11                                  25D    Pr.sub.2 NH                                                                             150        11       MnAPSO-11                                  26D    Pr.sub.2 NH                                                                             200        4        MnAPSO-11;                                                                     MnAPSO-39                                  27D    Pr.sub.2 NH                                                                             200        11       MnAPSO-11;                                                                     MnAPSO-39                                  28D    Pr.sub.2 NH                                                                             100        4        --.sup.3                                   29D    Pr.sub.2 NH                                                                             100        11       --.sup.3                                   ______________________________________                                          .sup.1 The reaction mixture comprised: 1.0 R: 0.2 MnO: 0.9 Al.sub.2            O.sub.3 : 0.9 P.sub.2 O.sub.5 : 0.2 SiO.sub.2 : 50 H.sub.2 O where "R" is      the template, as identified in Table IID.                                      .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the predominant species observed.                                    .sup.3 No MnAPSO products were observed by xray analysis.                

                  TABLE III-D                                                      ______________________________________                                                                             MnAPSO                                     Example.sup.1                                                                         Template Temp (°C.)                                                                         Time (days)                                                                             Product.sup.2                              ______________________________________                                         30D    Pr.sub.3 N .sup.                                                                        150        4        MnAPSO-5                                   31D    Pr.sub.3 N .sup.                                                                        150        11       MnAPSO-5                                   32D    Pr.sub.3 N .sup.                                                                        200        4        MnAPSO-5                                   33D    Pr.sub.3 N .sup.                                                                        200        11       MnAPSO-5                                   34D    Pr.sub.3 N .sup.                                                                        100        4        --.sup.3                                   35D    Pr.sub.3 N .sup.                                                                        100        11       --.sup.3                                   36D    TBAOH    150        4        --.sup.3                                   37D    TBAOH    150        10       --.sup.3                                   38D    TBAOH    200        4        MnAPSO-5                                   39D    TBAOH    200        10       MnAPSO-5                                   40D    C-hex .sup.                                                                             150        3        MnAPSO-13                                  41D    C-hex .sup.                                                                             150        9        MnAPSO-44;                                                                     MnAPSO-13                                  42D    C-hex .sup.                                                                             200        3        MnAPSO-5;                                                                      MnAPSO-44                                  43D    C-hex .sup.                                                                             200        9        MnAPSO-5;                                                                      MnAPSO-44                                  ______________________________________                                          The reaction mixture comprised:                                                (a)Examples 30D to 35D: 1.0 Pr.sub.3 N; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ;        0.9 P.sub.2 O.sub.5 ; 0.2 SiO.sub.2 ; 50 H.sub.2 O                             (b)Examples 36D to 39D: 2.0 TBAOH; 0.4 MnO; 0.8 Al.sub.2 O.sub.3 ; 1.0         P.sub.2 O.sub.5 ; 0.4 SiO.sub.2 ; 50 H.sub.2 O                                 (c)Examples 40D to 43D: 1.0 Chex; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ; 0.9          P.sub.2 O.sub.5 ; 0.6 SiO.sub.2 ; 50 H.sub.2 O                                 .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the predominant species observed.                                    .sup.3 No MnAPSO products were observed by xray analysis.                

                  TABLE IV-D                                                       ______________________________________                                                                             MnAPSO                                     Example.sup.1                                                                         Template Temp (°C.)                                                                        Time (days)                                                                              Product.sup.2                              ______________________________________                                         44D    TPAOH    150       2         MnAPSO-5                                   45D    TPAOH    200       2         MnAPSO-5                                   46D    TMAOH    150       4         MnAPSO-20                                  47D    TMAOH    200       4         MnAPSO-20                                  48D    DEA      150       9         MnAPSO-47                                  49D    DEA      150       18        MnAPSO-47                                  .sup. 50D.sup.4                                                                       Pr.sub.2 NH                                                                             150       4         MnAPSO-31                                  .sup. 51D.sup.4                                                                       Pr.sub.2 NH                                                                             150       10        MnAPSO-31;                                                                     MnAPSO-46                                  .sup. 52D.sup.4                                                                       Pr.sub.2 NH                                                                             200       4         MnAPSO-31;                                                                     MnAPSO-11                                  .sup. 53D.sup.4                                                                       Pr.sub.2 NH                                                                             200       10        MnAPSO-31;                                                                     MnAPSO-11                                  .sup. 54D.sup.4                                                                       Pr.sub.2 NH                                                                             150       2         MnAPSO-31                                  .sup. 55D.sup.4                                                                       Pr.sub.2 NH                                                                             150       2         MnAPSO-31                                  .sup. 56D.sup.4                                                                       Pr.sub.2 NH                                                                             200       2         MnAPSO-31;                                                                     MnAPSO-11                                  57D    Pr.sub.2 NH                                                                             200       25        MnAPSO-11; MnAPSO-5                                                            MnAPSO-39;                                                                     MnAPSO-46                                  58D    Quin     225       5         MnAPSO-16;                                                                     MnAPSO-35                                  .sup. 59D.sup.5                                                                       Pr.sub.3 N                                                                              150       2         MnAPSO-36                                  .sup. 60D.sup.5                                                                       Pr.sub.3 N                                                                              150       7         MnAPSO-36;                                                                     MnAPSO-5                                   .sup. 61D.sup.5                                                                       Pr.sub.3 N                                                                              200       2         MnAPSO-36;                                                                     MnAPSO-5                                   .sup. 62D.sup.5                                                                       Pr.sub.3 N                                                                              200       7         MnAPSO-36;                                                                     MnAPSO-5                                   63D    C-hex    225       5         MnAPSO-5;                                                                      MnAPSO-44                                  64D    C-hex    200       4         MnAPSO-44                                  ______________________________________                                          .sup.1 The reaction mixture comprised: 1.0 R; 0.2 MnO; 0.9 Al.sub.2            O.sub.3 ; 0.9 P.sub.2 O.sub.5 ; 0.6 SiO.sub.2 ; 50 H.sub.2 O where R is a      above identified and except than in examples 48D, 49D, 57D and 64D the         moles of "R" was 2.0 and in example 58D the coefficient for P.sub.2            O.sub.5 was 1.0 instead of 0.9.                                                .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species where identified the first species       listed is the predominant species observed.                                    .sup.3 No MnAPSO products were observed by xray analysis.                      .sup.4 Seed crystals of AlPO.sub.4 -31 were employed (U.S. Pat. No.            4,310,440).                                                                    .sup.5 Seed crystals of MnAPO36 were employed, as disclosed in U.S. Ser.       No. 514,334; filed July 15, 1983.                                        

EXAMPLE 65D

(a) Samples of the MnAPSO products were calcined in air or nitrogen to remove at least part of the organic templating agent of the product. The example in which a given MnAPSO product was prepared is given in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned MnAPSO molecular sieves are set forth hereinafter:.

(a) MnAPSO-5 (Example 31D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       102      -183    8.9                                       O.sub.2  3.46       750      -183    10.8                                      n-butane 4.3        504      23.0    4.4                                       cyclohexane                                                                             6.0         65      23.4    5.4                                       H.sub.2 O                                                                               2.65          4.6   23.0    8.1                                       H.sub.2 O                                                                               2.65         19.5   23.0    17.1                                      ______________________________________                                          *MnAPSO-5 was calcined at 600° C. in air for 4 hours.             

The above data demonstrate that the pore size of the calcined MnAPSO-5 product is greater than about 6.2 Å.

(b) MnAPSO-11 (Example 24D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       106      -183    7.0                                       O.sub.2  3.46       744      -183    11.1                                      neopentane                                                                              6.2        741      25.3    2.5                                       isobutane                                                                               5.0        740      24.2    3.5                                       cyclohexane                                                                             6.0         82      23.9    10.7                                      H.sub.2 O                                                                               2.65          4.6   24.9    5.1                                       H.sub.2 O                                                                               2.65        19      24.8    14.9                                      ______________________________________                                          *MnAPSO was calcined at 600° C. in air for 2 hours.               

The above data demonstrate that the pore size of the calcined MnAPSO-11 product is greater than about 6.0 Å.

(c) MnAPSO-20 (Example 46D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       102      -183    0.7                                       O.sub.2  3.46       744      -183    1.2                                       H.sub.2 O                                                                               2.65          4.6   23.3    9.0                                       H.sub.2 O                                                                               2.65        19      23.2    13.7                                      ______________________________________                                          *MnAPSO was calcined at 500° C. in air for 1 hour.                

The above data demonstrate that the pore size of the calcined MnAPSO-20 product is greater than about 2.65 Å and less than about 3.46 Å.

(d) MnAPSO-31 (Example 55D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       105      -183    5.6                                       O.sub.2  3.46       741      -183    9.7                                       Neopentane                                                                              6.2        739      23.5    4.6                                       H.sub.2 O                                                                               2.65          4.6   23.8    5.8                                       H.sub.2 O                                                                               2.65        20      24.0    15.5                                      ______________________________________                                          *MnAPSO-31 was calcined at 500° C. in air for 1.5 hours.          

The above data demonstrate that the pore size of the calcined MnAPSO-31 product is greater than about 6.2 Å.

(e) MnAPSO-34 (Example 11D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       103      -183    11.4                                      O.sub.2  3.46       731      -183    15.6                                      isobutane                                                                               5.0        741      24.5     0.8                                      n-hexane 4.3        103      24.4     4.6                                      H.sub.2 O                                                                               2.65          4.6   24.4    15.2                                      H.sub.2 O                                                                               2.65         18.5   23.9    24.4                                      ______________________________________                                          *MnAPSO-34 was calcined at 425° C. in nitrogen for 2 hours.       

The above data demonstrate that the pore size of the calcined MnAPSO-34 product is about 4.3 Å.

(f) MnAPSO-35 (Example 21D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       103      -183    1.8                                       O.sub.2  3.46       731      -183    2.6                                       n-hexane 4.3        103      24.4    0.8                                       H.sub.2 O                                                                               2.65          4.6   24.4    9.9                                       H.sub.2 O                                                                               2.65         18.5   23.9    15.9                                      ______________________________________                                          *MnAPSO-35 was calcined at 500° C. in nitrogen for 2 hours.       

The above data demonstrate that the pore size of the calcined MnAPSO-35 product is about 4.3 Å.

(g) MnAPSO-44 (Example 64D):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       102      -183    18.2                                      O.sub.2  3.46       744      -183    20.1                                      n-hexane 4.3         95      23.6     1.3                                      isobutane                                                                               5.0        746      24.1     0.5                                      H.sub.2 O                                                                               2.65          4.6   24.8    22.7                                      H.sub.2 O                                                                               2.65        19      29.8    27.7                                      ______________________________________                                          *MnAPSO-44 was calcined at 500° C. in air for 1.0 hour.           

The above data demonstrate that the pore size of the calcined MnAPSO-44 product about 4.3 Å.

EXAMPLE 66D

Samples of the as-synthesized products of certain examples were subjected to chemical analysis. The example in which a given MnAPSO was prepared is noted in parenthesis. The chemical analysis for these MnAPSOs was as follows:

(a) The chemical analysis for MnAPSO-5 (Example 31D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.8                                                             P.sub.2 O.sub.5                                                                              46.4                                                             MnO            4.1                                                             SiO.sub.2      3.0                                                             Carbon         5.2                                                             LOI*          14.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al₂ O₃ : 0.327 P₂ O₅ : 0.050 SiO₂ ; and a formula (anhydrous basis) of:

    0.05R(Mn.sub.0.04 Al.sub.0.45 P.sub.0.47 Si.sub.0.04)O.sub.2

(b) The chemical analysis of MnAPSO-11 (Example 24D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.5                                                             P.sub.2 O.sub.5                                                                              46.7                                                             MnO            4.3                                                             SiO.sub.2      2.1                                                             Carbon         4.1                                                             LOI*          14.0                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.061 MnO; 0.319 Al₂ O₃ ; 0.329 P₂ O₅ ; 0.035 SiO₂ ; and a formula (anhydrous basis) of:

    0.06R(Mn.sub.0.04 Al.sub.0.46 P.sub.0.47 Si.sub.0.03)O.sub.2

(c) The chemical analysis for MnAPSO-20 (Example 46D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.3                                                             P.sub.2 O.sub.5                                                                              39.6                                                             MnO            4.6                                                             SiO.sub.2      8.0                                                             Carbon         8.4                                                             LOI*          19.4                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.065 MnO; 0.268 Al₂ O₃ : 0.279 P₂ O₅ : 0.133 SiO₂ ; and a formula (anhydrous basis) of:

    0.18R(Mn.sub.0.05 Al.sub.0.41 P.sub.0.43 Si.sub.0.10)O.sub.2

(d) The chemical analysis of MnAPSO-31 was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             31.8                                                             P.sub.2 O.sub.5                                                                              43.8                                                             MnO            3.2                                                             SiO.sub.2      2.6                                                             Carbon         2.9                                                             LOI*          16.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al₂ O₃ ; 0.309 P₂ O₅ ; 0.043 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R(Mn.sub.0.04 Al.sub.0.47 P.sub.0.46 Si.sub.0.03)O.sub.2

(e) The chemical analysis of MnAPSO-34 (Example 6D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             25.0                                                             P.sub.2 O.sub.5                                                                              35.8                                                             MnO            7.9                                                             SiO.sub.2     11.6                                                             Carbon         3.3                                                             LOI*          19.7                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.11 MnO; 0.25 Al₂ O₃ ; 0.19 P₂ O₅ ; 0.19 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R(Mn.sub.0.09 Al.sub.0.38 P.sub.0.39 Si.sub.0.15)O.sub.2

(f) The chemical analysis of MnAPSO-35 (Example 23D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             25.2                                                             P.sub.2 O.sub.5                                                                              41.3                                                             MnO            7.1                                                             SiO.sub.2      4.2                                                             Carbon        12.8                                                             LOI*          21.3                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.100 MnO; 0.247 Al₂ O₃ ; 0.291 P₂ O₅ ; 0.07 SiO₂ ; and a formula (anhydrous basis) of:

    0.13R(Mn.sub.0.08 Al.sub.0.40 P.sub.0.47 Si.sub.0.06)O.sub.2

(g) The chemical analysis of MnAPSO-36 (Example 59D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.7                                                             P.sub.2 O.sub.5                                                                              37.2                                                             MnO            4.6                                                             SiO.sub.2      9.5                                                             Carbon         3.0                                                             LOI*          19.6                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios anhydrous basis) of: 0.065 MnO; 0.272 Al₂ O₃ ; 0.262 P₂ O₅ ; 0.158 SiO₂ ; and a formula (anhydrous basis) of:

    0.03R(Mn.sub.0.05 Al.sub.0.42 P.sub.0.41 Si.sub.0.12)O.sub.2

(h) The chemical analysis of MnAPSO-44 (Example 64D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             25.8                                                             P.sub.2 O.sub.5                                                                              36.6                                                             MnO            4.4                                                             SiO.sub.2      9.7                                                             Carbon         2.5                                                             LOI*          23.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.062 MnO; 0.253 Al₂ O₃ ; 0.258 P₂ O₅ ; 0.161 SiO₂ ;; and a formula (anhydrous basis) of:

    0.04R(Mn.sub.0.05 Al.sub.0.41 P.sub.0.41 Si.sub.0.13)O.sub.2

(i) The chemical analysis of MnAPSO-47 (Example 49D) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.6                                                             P.sub.2 O.sub.5                                                                              36.2                                                             MnO            5.0                                                             SiO.sub.2      5.7                                                             Carbon         9.9                                                             LOI*          25.1                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.071 MnO; 0.271 Al₂ O₃ ; 0.255 P₂ O₅ ; 0.095 SiO₂ ; and a formula (anhydrous basis) of:

    0.17R(Mn.sub.0.06 Al.sub.0.44 P.sub.0.42 Si.sub.0.08)O.sub.2

EXAMPLE 67D

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of certain examples, as identified in parenthesis hereinafter. Analysis of crystals having a morphology characteristic of each MnAPSO product gave the following analysis based on relative peak heights:

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         (a) MnAPSO-5 (Example 4D):                                                     Mn        0.5                                                                  Al        8.0                                                                  P         9.5                                                                  Si        0.7                                                                  (b) MnAPSO-11 (Example 24D):                                                   Mn        1.0                                                                  Al        8.0                                                                  P         9.5                                                                  Si        1.5                                                                  (c) MnAPSO-20 (Example 46D):                                                   Mn        0.8                                                                  Al        8.2                                                                  P         9.4                                                                  Si        1.7                                                                  (d) MnAPSO-34 (Example 6D):                                                    Mn        1.3                                                                  Al        7.0                                                                  P         9.0                                                                  Si        1.5                                                                  (e) MnAPSO-35 (Example 23D):                                                   Mn        1.0                                                                  Al        7.0                                                                  P         10.0                                                                 Si        1.2                                                                  (f) MnAPSO-36 (Example 59D):                                                   Mn        0.8                                                                  Al        9.3                                                                  P         9.9                                                                  Si        1.6                                                                  (g) MnAPSO-44 (Example 42D):                                                   Mn        0.7                                                                  Al        9.0                                                                  P         10.0                                                                 Si        1.7                                                                  (h) MnAPSO-44 (Example 64D):                                                   Mn        1.1                                                                  Al        8.7                                                                  P         10.0                                                                 Si        5.6                                                                  (i) MnAPSO-47 (Example 49D):                                                   Mn        1.0                                                                  Al        9.0                                                                  P         9.5                                                                  Si        1.9                                                                  ______________________________________                                    

EXAMPLE 68D

(a) The MnAPSO-5, prepared in Example 31D, was subjected to x-ray analysis. The MnAPSO-5 was impure but the major phase was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          6.9*          12.81   13                                                       7.5           11.79   100                                                      8.0*          11.05   5                                                        9.1*          9.72    4                                                        9.3*          9.51    4                                                       13.0           6.81    14                                                       13.7*         6.46    3                                                       15.0           5.91    27                                                       16.5*         5.37    3                                                        18.5*         4.80    7                                                       19.8           4.48    43                                                      21.0           4.23    58                                                      22.3           3.99    75                                                      24.7           3.60    6                                                       25.9           3.440   42                                                      29.0           3.079   18                                                      30.0           2.979   34                                                      33.6           2.667   8                                                       34.5           2.600   21                                                      36.9           2.436   4                                                       37.7           2.386   10                                                      41.5           2.176   5                                                       42.1           2.146   5                                                       42.2           2.141   5                                                       42.6           2.122   5                                                       43.5           2.080   3                                                       44.9           2.019   3                                                       47.5           1.914   7                                                       51.4           1.778   5                                                       51.9           1.762   3                                                       55.5           1.656   5                                                       ______________________________________                                          *Peak may contain an impurity                                            

(b) A portion of the as-synthesized MnAPSO-5 of part (a) was calcined in air at 500° C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          7.4           11.95   100                                                     *7.8           11.33   4                                                       12.9           6.86    25                                                      15.0           5.91    21                                                      *16.5          5.37    3                                                       *16.7          5.31    3                                                       *17.5          5.07    5                                                       19.8           4.48    40                                                      21.2           4.19    40                                                      22.5           3.95    43                                                      26.0           3.427   30                                                      29.1           3.069   11                                                      30.1           2.969   35                                                      33.7           2.660   5                                                       34.6           2.592   19                                                      37.1           2.423   4                                                       37.9           2.374   6                                                       42.5           2.127   4                                                       43.1           2.099   3                                                       46.0           1.973   3                                                       47.9           1.899   5                                                       55.8           1.647   4                                                       ______________________________________                                          *Peak may contain an impurity                                            

(c) The species denominated herein as MnAPSO-5 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empiracal chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-5 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V-D as follows:

                  TABLE V-D                                                        ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         7.3-7.7     12.11-11.48                                                                              vs                                                       14.7-15.1   6.03-5.87 m                                                        19.6-19.9   4.53-4.46 m                                                        20.8-21.3   4.27-4.17 m                                                        22.1-22.6   4.02-3.93 m                                                        29.8-30.2   2.998-2.959                                                                              m                                                        ______________________________________                                    

(d) All of the MnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VI-D below:

                  TABLE VI-D                                                       ______________________________________                                         2θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         7.3-7.7       12.11-11.48                                                                              100                                                    12.7-13.0     6.97-6.81 14-27                                                  14.7-15.1     6.03-5.87 20-60                                                  19.6- 19.9    4.53-4.46 36-51                                                  20.8-21.3     4.27-4.17 29-58                                                  22.1-22.6     4.02-3.93 30-75                                                  24.5-24.7     3.63-3.60 4-6                                                    25.7-26.1     3.466-3.414                                                                              25-42                                                  28.8-29.2     3.100-3.058                                                                              10-30                                                  29.8-30.2     2.998-2.959                                                                              34-50                                                  33.4-33.8     2.683-2.652                                                                               4-10                                                  34.3-34.7     2.614-2.585                                                                              19-44                                                  36.7-37.2     2.449-2.417                                                                              3-4                                                    37.5-38.0     2.398-2.368                                                                               5-20                                                  41.3-41.5     2.186-2.176                                                                              3-5                                                    41.9-42.1     2.156-2.146                                                                              4-5                                                    42.0-42.2     2.151-2.141                                                                              3-5                                                    42.4-42.6     2.132-2.122                                                                              3-5                                                    43.1-43.5     2.099-2.080                                                                              3-5                                                    44.7-44.9     2.027-2.019                                                                              3-5                                                    46.0-46.1     1.973-1.969                                                                              3-4                                                    47.3-47.6     1.922-1.910                                                                              5-7                                                    47.9-48.0     1.899-1.895                                                                              4-5                                                    51.2-51.4     1.784-1.778                                                                              5-7                                                    51.7-51.9     1.768-1.762                                                                              3-5                                                    55.3-55.9     1.661-1.645                                                                              2-7                                                    ______________________________________                                    

EXAMPLE 69D

(a) MnAPSO-11, as prepared in example 24D, was subjected to x-ray analysis. The MnAPSO-11 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          8.1           10.92   36                                                       9.5           9.31    61                                                      13.1           6.76    19                                                      15.7           5.64    36                                                      16.2           5.47    10                                                      19.1           4.65    13                                                      20.5           4.33    45                                                      21.1           4.21    100                                                     22.2           4.00    55                                                      22.5           3.95    52                                                      22.7           3.92    61                                                      23.2           3.83    71                                                      24.5           3.63    13                                                      24.8           3.59    16                                                      25.0           3.562   13                                                      26.4           3.38    26                                                      28.3           3.153   13                                                      28.6           3.121   23                                                      29.5           3.028   13                                                      31.5           2.84    16                                                      32.8           2.730   23                                                      34.2           2.622   16                                                      35.4           2.54    10                                                      35.8           2.508   10                                                      36.3           2.475   10                                                      37.5           2.398   13                                                      37.8           2.370   16                                                      39.4           2.287   10                                                      42.9           2.108   10                                                      44.8           2.023   10                                                      48.8           1.866    3                                                      50.6           1.804   10                                                      54.6           1.681   10                                                      ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-11 of part (a) was calcined in air at 600° C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          8.1           10.92   33                                                       9.8           9.03    60                                                      11.8           7.50    13                                                      12.8           6.92    27                                                      13.5           6.56    13                                                      14.8           5.99    sh                                                      16.1           5.51    67                                                      19.5           4.55    27                                                      19.9           4.46    40                                                      20.4           4.35    33                                                      21.5           4.13    73                                                      21.8           4.08    100                                                     22.2           4.00    73                                                      22.4           3.97    80                                                      23.5           3.79    73                                                      24.3           3.66    27                                                      25.8           3.453   33                                                      26.7           3.339   27                                                      27.3           3.267   33                                                      27.8           3.209   33                                                      28.5           3.132   27                                                      29.5           3.028   33                                                      29.8           2.998   40                                                      30.4           2.940   27                                                      31.8           2.814   20                                                      32.6           2.747   33                                                      34.0           2.637   20                                                      35.5           2.529   27                                                      37.1           2.423   20                                                      37.4           2.404   20                                                      38.2           2.356   20                                                      38.6           2.332   27                                                      41.0           2.201   20                                                      ______________________________________                                    

(c) The species denominated herein as MnAPSO-11 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-11 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-D as follows:

                  TABLE VII-D                                                      ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         9.4-9.8     9.41-9.03 m                                                        16.1-16.2   5.50-5.47 vw-m                                                     21.0-21.5   4.23-4.13  m-vs                                                    22.1-22.2   4.02-4.00 m                                                        22.4-22.5   3.97-3.95 m-s                                                      23.1-23.5   3.85-3.79 m                                                        ______________________________________                                    

(d) All of the MnAPSO-11 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VIII-D below:

                  TABLE VIII-D                                                     ______________________________________                                         2θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         8.0-8.1       11.05-10.92                                                                              31-36                                                  9.4-9.8       9.41-9.03 56-61                                                  11.8          7.50      13                                                     12.8-13.1     6.92-6.76 17-27                                                  13.5          6.56      13                                                     14.8          5.99      sh                                                     15.6-15.7     5.68-5.64 33-36                                                  16.1-16.2     5.50-5.47  8-67                                                  19.0-19.5     4.68-4.55  8-27                                                  19.9          4.46      40                                                     20.4-20.5     4.35-4.33 33-45                                                  21.0-21.5     4.23-4.13  73-100                                                21.8          4.08      100                                                    22.1-22.2     4.02-4.00 55-73                                                  22.4-22.5     3.97-3.95 52-80                                                  22.6-22.7     3.93-3.92 61                                                     23.1-23.5     3.85-3.79 69-73                                                  24.3-24.5     3.66-3.63 11-27                                                  24.7-24.8     3.60-3.59 14-16                                                  24.9-25.0      3.58-3.562                                                                              sh-13                                                  25.8          3.453     33                                                     26.3-26.7     3.389-3.339                                                                              25-27                                                  27.3          3.267     33                                                     27.8          3.209     33                                                     28.2-28.3     3.164-3.153                                                                              11-13                                                  28.5-28.6     3.132-3.121                                                                              22-27                                                  29.4-29.5     3.038-3.028                                                                              11-33                                                  29.8          2.998     40                                                     30.4          2.940     27                                                     31.4-31.8     2.849-2.814                                                                              14-20                                                  32.6-32.8     2.747-2.730                                                                              19-33                                                  34.0-34.2     2.637-2.622                                                                              14-20                                                  35.3-35.5     2.543-2.529                                                                              sh-27                                                  35.7-35.8     2.515-2.508                                                                               8-10                                                  36.2-26.3     2.481-2.475                                                                               8-10                                                  37.1          2.423     20                                                     37.4-37.5     2.404-2.398                                                                              11-20                                                  37.7-37.8     2.386-2.380                                                                              16-17                                                  38.2          2.356     20                                                     38.6          2.332     27                                                     39.3-39.4     2.292-2.287                                                                               8-10                                                  41.0          2.201     20                                                     42.8-42.9     2.113-2.108                                                                               8-10                                                  44.7-44.8     2.027-2.023                                                                               8-10                                                  48.7-48.8     1.870-1.866                                                                              3-5                                                    50.5-50.6     1.807-1.804                                                                               8-10                                                  54.5-54.6     1.684-1.681                                                                               8-10                                                  ______________________________________                                    

EXAMPLE 70D

(a) MnAPSO-16, as prepared in example 14D was subjected to x-ray analysis. The MnAPSO-16 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          8.6*          10.28    8                                                      11.0*          8.04    23                                                      11.4           7.76    48                                                      13.3*          6.66    11                                                      15.9*          5.57     5                                                      17.3*          5.13    24                                                      17.7*          5.01     8                                                      18.7           4.75    40                                                      21.1*          4.21    19                                                       21.9**        4.06    100                                                     23.0           3.87    13                                                      23.2*          3.83    10                                                      23.7*          3.75     5                                                      25.1           3.548    5                                                       26.6**        3.351   26                                                      26.7*          3.339   (sh)                                                    27.8           3.209    5                                                      28.8*          3.100   15                                                      29.0           3.079   15                                                      29.8           2.998   24                                                      32.0*          2.797   16                                                      32.6           2.747    7                                                       34.7**        2.585   10                                                      35.7*          2.515    5                                                      37.8           2.380   11                                                      39.7           2.270    5                                                      42.0*          2.151    5                                                      44.2           2.049    5                                                       48.5**        1.877   10                                                      49.4*          1.845    5                                                      52.4           1.746    5                                                      54.7           1.678    5                                                      ______________________________________                                          *Impurity Peak                                                                 **Peak may contain impurity                                              

(b) A portion of the as-synthesized MnAPSO-16 of part (a) was calcined in nitrogen at 600° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                         11.5           7.69    100                                                      13.3*         6.66     9                                                      18.6           4.77    25                                                       20.3*         4.37    44                                                       20.5*         4.33    41                                                       21.5*         4.13    66                                                       21.9**        4.06    72                                                      22.9           3.88    31                                                       23.5*         3.79    13                                                       26.5**        3.363   31                                                      27.9           3.198   13                                                      29.0           3.079   19                                                      29.7           3.008   34                                                      32.6           2.747   13                                                       34.7**        2.585   13                                                       35.6*         2.522   16                                                      37.8           2.380   13                                                       48.2**        1.888    9                                                      ______________________________________                                          *Impurity Peak                                                                 **Peak may contain impurity                                              

(c) The species denominated herein as MnAPSO-16 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-16 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-D as follows:

                  TABLE IX-D                                                       ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         11.4-11.5   7.76-7.69 m-vs                                                     18.6-18.7   4.77-4.75 m                                                        21.9        4.06      m-vs                                                     22.9-23.0   3.88-3.87 w-m.sup.                                                 26.5-26.6   3.363-3.351                                                                              m                                                        29.7-29.8   3.008-2.998                                                                              m                                                        ______________________________________                                    

(d) All of the MnAPSO-16 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table X-D below:

                  TABLE X-D                                                        ______________________________________                                         2θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         11.4-11.5     7.76-7.69  48-100                                                18.6-18.7     4.77-4.75 25-40                                                   21.9*        4.06      72-80                                                  22.9-23.0     3.88-3.87 13-31                                                   26.5-26.6*   3.363-3.351                                                                              26-31                                                  27.8-27.9     3.209-2.198                                                                               5-13                                                  29.0          3.079     15-19                                                  29.7-29.8     3.008-2.998                                                                              24-34                                                  32.6          2.747      7-14                                                   34.7*        2.585      9-14                                                  37.8          2.380     11-15                                                  39.7          2.270     5-6                                                    44.2          2.049     5-6                                                     48.2-48.5*   1.888-1.877                                                                               9-12                                                  49.4          1.845     4-5                                                    52.4          1.746     4-5                                                    54.7          1.678     4-5                                                    ______________________________________                                          *Peak might contain an impurity                                          

EXAMPLE 71D

(a) MnAPSO-20, as prepared in example 46D was subjected to x-ray analysis. The MnAPSO-20 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                         14.0           6.35    49                                                      19.8           4.49    43                                                      22.1           4.02    3                                                        23.7*         3.75    1                                                       24.3           3.67    100                                                     28.1           3.177   13                                                      31.5           2.842   11                                                      34.6           2.595   16                                                      37.5           2.400   2                                                       40.1           2.247   4                                                       42.7           2.118   4                                                       47.4           1.917   4                                                       51.8           1.764   7                                                       ______________________________________                                          *Peak may contain an impurity                                            

(b) A portion of the as-synthesized MnAPSO-20 of part (a) was calcined in air at 500° C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ     d, (Å)                                                                             Relative Intensity                                        ______________________________________                                          7.1         12.51    2                                                        14.0         6.33    100                                                       19.8         4.48    40                                                        22.2         4.00     4                                                        24.3         3.66    99                                                        28.2         3.168   17                                                        31.6         2.835   15                                                        34.7         2.589   17                                                        40.2         2.243    3                                                        42.7         2.116    4                                                        47.5         1.913    4                                                        ______________________________________                                    

(c) The species denominated herein as MnAPSO-20 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-20 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-D as follows:

                  TABLE XI-D                                                       ______________________________________                                         2θ     d, (Å) Relative Intensity                                     ______________________________________                                         13.904-13.998                                                                               6.3692-6.3263                                                                             m-vs                                                   19.723-19.818                                                                               4.5011-4.4918                                                                             m                                                      24.223-24.329                                                                               3.6742-3.6584                                                                             vs                                                     28.039-28.163                                                                               3.1822-3.1684                                                                             w                                                      31.434-31.560                                                                               2.8458-2.8348                                                                             w                                                      34.527-34.652                                                                               2.5976-2.5866                                                                             w                                                      ______________________________________                                    

(d) All of the MnAPSO-20 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XII-D below:

                  TABLE XII-D                                                      ______________________________________                                         2θ       d, (Å) I/Io × 100                                     ______________________________________                                         13.904-13.998  6.3692-6.3263                                                                              49-100                                              19.723-19.818  4.5011-4.4918                                                                             40-43                                                22.091-22.200  4.0236-4.0041                                                                             3-4                                                  24.223-24.329  3.6742-3.6584                                                                              99-100                                              28.039-28.163  3.1822-3.1684                                                                             13-17                                                31.434-31.560  2.8458-2.8348                                                                             11-15                                                34.527-34.652  2.5976-2.5886                                                                             15-17                                                34.413-27.465  2.2501-2.4004                                                                             2                                                    40.071-40.207  2.2501-2.2428                                                                             3-4                                                  42.627-42.730  2.1209-2.1160                                                                             3-4                                                  47.383-47.519  1.9185-1.9134                                                                             3-4                                                  51.790-51.840  1.7652-1.7636                                                                             7                                                    ______________________________________                                    

EXAMPLE 72D

(a) MnAPSO-31, as prepared in example 54D was subjected to x-ray analysis. MnAPSO-31 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          7.9           11.22   4                                                        8.6           10.27   61                                                      17.2           5.17    5                                                       18.5           4.81    4                                                       20.4           4.36    49                                                      21.2           4.19    4                                                       22.0           4.04    30                                                      22.1           4.02    32                                                      22.7           3.92    100                                                     25.3           3.526   5                                                       25.8           3.459   3                                                       28.1           3.181   12                                                      29.8           2.995   6                                                       31.8           2.812   22                                                      35.2           2.548   9                                                       36.2           2.482   3                                                       37.3           2.411   3                                                       37.8           2.382   3                                                       38.3           2.353   3                                                       38.4           2.346   3                                                       39.4           2.285   3                                                       39.8           2.266   3                                                       40.3           2.241   3                                                       46.8           1.942   3                                                       48.8           1.866   2                                                       51.8           1.766   5                                                       55.6           1.654   2                                                       ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-31 of part (a) was calcined in air at 500° C. for about 1.5 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          8.6           10.31   58                                                      14.8           5.98    4                                                       17.1           5.18    9                                                       18.5           4.81    4                                                       20.4           4.36    52                                                      22.1           4.03    44                                                      22.7           3.92    100                                                     25.3           3.526   7                                                       25.8           3.460   8                                                       28.1           3.181   15                                                      29.8           2.998   11                                                      31.1           2.879   3                                                       31.8           2.811   33                                                      35.3           2.546   11                                                      36.3           2.477   6                                                       37.3           2.409   3                                                       37.8           2.383   3                                                       38.3           2.348   3                                                       39.4           2.289   4                                                       40.3           2.236   3                                                       45.4           2.000   3                                                       46.8           1.942   5                                                       47.6           1.909   4                                                       48.9           1.864   3                                                       51.7           1.767   6                                                       ______________________________________                                    

(c) The species denominated herein as MnAPSO-31 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-31 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-D as follows:

                  TABLE XIII-D                                                     ______________________________________                                         2θ     d, (Å)  Relative Intensity                                    ______________________________________                                         8.482-9.501  10.4240-9.3084                                                                             m                                                     20.222-20.353                                                                               4.3913-4.3632                                                                              m                                                     21.879-21.993                                                                               4.0622-4.0415                                                                              m                                                     22.071-22.088                                                                               4.0272-4.0242                                                                              m                                                     22.587-22.698                                                                               3.9364-3.9174                                                                              vs                                                    31.724-31.836                                                                               2.8546-2.8108                                                                              m                                                     ______________________________________                                    

(d) All of the MnAPSO-31 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:

                  TABLE XIV-D                                                      ______________________________________                                         2θ       d, (Å) I/Io × 100                                     ______________________________________                                         7.694-7.883   11.4904-11.2145                                                                            2-4                                                  8.482-9.501   10.4240-9.3084                                                                             58-66                                                14.756-14.822 6.0034-5.9767                                                                              2-4                                                  17.016-17.158 5.2105-5.1679                                                                              5-9                                                  18.310-18.466 4.8451-4.8046                                                                              3-4                                                  20.222-20.353 4.3913-4.3632                                                                              45-52                                                21.032-21.221 4.2238-4.1867                                                                              4-5                                                  21.879-21.993 4.0622-4.0415                                                                              30-51                                                22.071-22.088 4.0272-4.0242                                                                              32-44                                                22.587-22.698 3.9364-3.9174                                                                              100                                                  23.164-23.190 3.8398-3.8355                                                                              2-3                                                  25.115-25-260 3.5457-3.5256                                                                              4-7                                                  25.663-25.757 3.4712-3.4588                                                                              3-8                                                  27.922-28.050 3.1953-3.1809                                                                              12-15                                                29.701-29.831 3.0078-2.9950                                                                               6-11                                                31.068-31.315 2.8785-2.8564                                                                              2-3                                                  31.724-31.836 2.8564-2.8108                                                                              21-33                                                35.117-35.251 2.5553-2.5460                                                                               9-11                                                35.871        2.5033      1                                                    36.070-36.261 2.4900-4730 2-6                                                  37.123-37.325 2.4217-2.4091                                                                              2-3                                                  37.628-27.763 2.3904-2.3822                                                                              2-3                                                  38.163-38.254 2.3581-2.3527                                                                              2-3                                                  38.334-38.367 2.3480-2.3461                                                                              3                                                    39.285-39.442 2.2933-2.2845                                                                              3-4                                                  39.654-39.772 2.2728-2.2663                                                                              2-4                                                  40.111-40.337 2.2480-2.2359                                                                              2-3                                                  45.179-45.354 2.0069-1.9996                                                                              2-3                                                  46.617-46.786 1.9483-1.9416                                                                              3-5                                                  47.454-47.631 1.9158-1.9091                                                                              2-4                                                  48.610- 48.846                                                                               1.8729-1.8644                                                                              2-3                                                  50.679-50.750 1.8012-1.7989                                                                              2                                                    51.588-51.766 1.7716-1.7659                                                                              4-6                                                  55.410-55.557 1.6581-1.6541                                                                              2                                                    ______________________________________                                    

EXAMPLE 73D

(a) MnAPSO-34, as prepared in example 11D was subjected to x-ray analysis. MnAPSO-34 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          9.6           9.21    100                                                     12.9           6.86    17                                                      14.2           6.24    15                                                      16.1           5.51    33                                                      18.1           4.90    23                                                      20.6           4.31    69                                                      22.3           3.99    10                                                      23.1           3.85     8                                                      25.2           3.534   25                                                      25.8           3.453   19                                                      27.5           3.243   10                                                      28.4           3.143   10                                                      29.5           3.028   10                                                      30.5           2.931   27                                                      31.2           2.867   23                                                      33.8           2.652    8                                                      34.3           2.614   12                                                      36.3           2.475    8                                                      43.0           2.103    6                                                      43.5           2.080    6                                                      47.5           1.914    6                                                      48.9           1.863    8                                                      50.9           1.794    6                                                      53.0           1.728    6                                                      55.7           1.650    6                                                      ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-34 of part (a) was calcined in nitrogen at 425° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ       d, (Å)                                                                             I/Io × 100                                        ______________________________________                                          9.6           9.21    100                                                     13.0           6.86    25                                                      14.1           6.28    5                                                       16.2           5.47    15                                                      17.9           4.96    15                                                      19.1           4.65    5                                                       20.8           4.27    37                                                      22.2           4.00    5                                                       22.4           3.97    5                                                       23.2           3.83    7                                                       25.2           3.534   15                                                      26.0           3.427   12                                                      27.7           3.220   4                                                       28.3           3.153   5                                                       29.7           3.008   4                                                       30.7           2.912   17                                                      31.3           2.849   11                                                      32.4           2.763   3                                                       34.6           2.592   5                                                       36.2           2.481   4                                                       38.8           2.321   3                                                       39.8           2.265   3                                                       43.1           2.099   3                                                       43.6           2.076   3                                                       47.8           1.903   1                                                       49.0           1.859   3                                                       51.0           1.791   3                                                       53.3           1.719   4                                                       54.6           1.681   3                                                       ______________________________________                                    

(c) The species denominated herein as MnAPSO-34 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-34 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-D as follows:

                  TABLE XV-D                                                       ______________________________________                                         2θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         9.4-9.6     9.41-9.21 vs                                                       15.9-16.2   5.57-5.47 m                                                        20.4-20.8   4.35-4.27 m-vs                                                     25.0-25.3   3.562-3.520                                                                              w-m                                                      31.0-31.3   2.885-2.858                                                                              w-m                                                      33.6-33.9   2.667-2.644                                                                              m                                                        ______________________________________                                    

(d) All of the MnAPSO-34 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:

                  TABLE XIV-D                                                      ______________________________________                                         2Θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         9.4-9.6       9.41-9.21 100                                                    12.7-13.0     6.97-6.86 17-25                                                  14.0-14.2     6.33-6.24 5-17                                                   15.9-16.2     5.57-5.47 15-44                                                  17.9-18.1     4.96-4.90 15-32                                                  19.1          4.65      5                                                      20.4-20.8     4.35-4.27 37-92                                                  22.1-22.3     4.02-3.99 5-16                                                   22.4          3.97      5                                                      22.9-23.2     3.88-3.83 7-16                                                   25.0-25.3     3.562-3.520                                                                              15-36                                                  25.8-26.0     3.453-3.427                                                                              12-19                                                  27.3-27.7     3.267-3.220                                                                              4-28                                                   28.2-28.5     3.164-3.132                                                                              5-16                                                   29.3-29.7     3.048-3.008                                                                              4-16                                                   30.3-30.7     2.950-2.912                                                                              10-17                                                  31.0-31.3     2.885-2.849                                                                              11-40                                                  32.4          2.763     3                                                      33.6-33.9     2.667-2.644                                                                              23-32                                                  34.3-34.6     2.614-2.592                                                                              5-12                                                   36.2-36.4     2.481-2.468                                                                              4-16                                                   38.8          2.321     3                                                      39.8          2.265     3                                                      43.0-43.1     2.103-2.099                                                                              3-12                                                   43.5-43.6     2.080-2.076                                                                              3-12                                                   47.4-47.8     1.918-1.903                                                                              1-12                                                   48.8-49.0     1.866-1.859                                                                              3-12                                                   50.8-51.0     1.797-1.791                                                                              3-12                                                   52.9-53.3     1.731-1.719                                                                              4-12                                                   54.6          1.681     3                                                      55.6-55.8     1.653-1.647                                                                              6-12                                                   ______________________________________                                    

EXAMPLE 74D

(a) MnAPSO-35, as prepared in example 22D was subjected to x-ray analysis. MnAPSO-35 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                          8.6          10.28   14                                                       10.9          8.12    45                                                       13.4          6.61    23                                                       15.9          5.57    11                                                       17.4          5.10    80                                                       17.8          4.98    16                                                       20.9          4.25    57                                                       21.9          4.06    100                                                      23.2          3.83    34                                                       24.8          3.59    9                                                        25.7          3.466   7                                                        26.9          3.314   21                                                       28.3          3.153   50                                                       29.1          3.069   11                                                       31.4          2.849   9                                                        32.1          2.788   41                                                       34.3          2.614   14                                                       34.9          2.571   7                                                        35.3          2.543   5                                                        35.8          2.508   7                                                        37.7          2.386   5                                                        39.5          2.281   5                                                        41.9          2.156   7                                                        42.7          2.118   7                                                        44.6          2.032   5                                                        47.6          1.910   7                                                        48.3          1.884   7                                                        49.5          1.841   7                                                        51.0          1.791   9                                                        55.0          1.670   5                                                        55.4          1.658   7                                                        ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-35 of part (a) was calcined in nitrogen at 500° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         8.6           10.28   27                                                       10.9          8.12    96                                                       11.4          7.76    14                                                       13.4          6.61    41                                                       15.8          5.61    14                                                       17.3          5.13    68                                                       17.7          5.01    sh                                                       20.8          4.27    64                                                       21.9          4.06    100                                                      23.3          3.82    32                                                       24.8          3.59    23                                                       25.7          3.466   18                                                       26.9          3.314   27                                                       28.3          3.153   59                                                       29.1          3.069   23                                                       31.4          2.849   18                                                       32.2          2.780   46                                                       34.2          2.622   18                                                       34.8          2.578   14                                                       35.8          2.508    9                                                       41.9          2.156    9                                                       42.5          2.127    9                                                       44.6          2.032    9                                                       47.4          1.918    9                                                       48.2          1.888    9                                                       49.4          1.845    9                                                       51.0          1.791   14                                                       55.2          1.664    9                                                       55.7          1.650    9                                                       ______________________________________                                    

(c) The species denominated herein as MnAPSO-35 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-35 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII-D as follows:

                  TABLE XVII-D                                                     ______________________________________                                         2Θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         10.8-11.0   8.19-8.04 m-vs                                                     13.4-13.7   6.61-6.46 m-s                                                      17.2-17.5   5.16-5.07 m-s                                                      20.8-21.0   4.27-4.23 m                                                        21.8-22.3   4.08-3.99 m-vs                                                     28.2-28.7   3.164-3.110                                                                              m                                                        ______________________________________                                    

(d) All of the MnAPSO-35 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XVIII-D below:

                  TABLE XVIII-D                                                    ______________________________________                                         2Θ      d, (Å)                                                                               I/Io × 100                                       ______________________________________                                         8.5-8.7       10.40-10.16                                                                              13-31                                                  10.8-11.0     8.19-8.04  44-100                                                11.4-11.5     7.76-7.69  8-14                                                  13.3-13.4     6.66-6.61 22-41                                                  13.4-13.7     6.61-6.46 31-81                                                  15.8-15.9     5.61-5.57 10-14                                                  17.2-17.5     5.16-5.07 38-82                                                  17.7-18.0     5.01-4.93 (sh)-18                                                20.8-21.0     4.27-4.23 44-46                                                  21.8-22.3     4.08-3.99  56-100                                                23.1-23.6     3.85-3.77 31-34                                                  24.7-25.2      3.60-3.534                                                                              13-31                                                  25.6-25.8     3.480-3.453                                                                               4-25                                                  26.8-27.4     3.326-3.255                                                                              19-44                                                  28.2-28.7     3.164-3.110                                                                              50-59                                                  29.0-29.6     3.079-3.018                                                                              10-31                                                  31.3-31.4     2.858-2.849                                                                               9-18                                                  32.0-32.8     2.797-2.730                                                                              31-46                                                  34.2-34.3     2.622-2.614                                                                              11-18                                                  34.8-34.9     2.578-2.571                                                                               4-14                                                  35.2-35.3     2.550-2.543                                                                              5-7                                                    35.7-35.8     2.515-2.508                                                                              4-9                                                    37.6-37.7     2.392-2.386                                                                              4-5                                                    39.4-39.5     2.287-2.281                                                                              4-7                                                    41.8-42.0     2.161-2.151                                                                              6-9                                                    42.5-42.8     2.127-2.113                                                                              5-9                                                    44.5-44.7     2.036-2.027                                                                              5-9                                                    47.4-47.7     1.918-1.907                                                                              6-9                                                    48.2-48.4     1.888-1.881                                                                              6-9                                                    49.4-49.6     1.845-1.838                                                                              6-9                                                    50.9-51.1     1.794-1.787                                                                               5-14                                                  54.9-55.2     1.672-1.664                                                                              5-9                                                    55.3-55.7     1.661-1.650                                                                              6-9                                                    ______________________________________                                    

EXAMPLE 75D

(a) MnAPSO-36, as prepared in example 59D was subjected to x-ray analysis. The MnAPSO-36 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         7.4           11.88   15                                                       7.9           11.22   100                                                      8.2           10.82   33                                                       13.5          6.55    5                                                        15.8          5.61    10                                                       16.4          5.41    31                                                       19.1          4.66    14                                                       20.7          4.28    34                                                       21.2          4.19    4                                                        21.7          4.10    16                                                       22.0          4.04    14                                                       22.5          3.96    15                                                       23.0          3.87    5                                                        23.9          3.73    6                                                        27.2          3.276   15                                                       27.9          3.193   3                                                        28.3          3.153   8                                                        29.0          3.079   7                                                        30.2          2.958   4                                                        30.3          2.951   4                                                        32.0          2.798   8                                                        34.8          2.579   7                                                        ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-36 of part (a) was calcined in air at 500° C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         7.1           12.39    5                                                       7.6           11.64   21                                                       8.0           11.11   100                                                      8.3           10.65   37                                                       13.6          6.53    17                                                       16.6          5.35    31                                                       19.4          4.57    17                                                       20.8          4.27    19                                                       21.9          4.06     8                                                       22.4          3.97    15                                                       22.7          3.92    11                                                       23.4          3.80     5                                                       23.9          3.73     7                                                       27.3          3.271   16                                                       28.3          3.159    6                                                       28.4          3.141    6                                                       29.1          3.074    7                                                       29.4          3.043    5                                                       32.0          2.798    6                                                       ______________________________________                                    

(c) The species denominated herein as MnAPSO-36 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-36 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-D as follows:

                  TABLE XIX-D                                                      ______________________________________                                         2Θ    d, (Å)  Relative Intensity                                     ______________________________________                                         7.596       11.6382     m                                                      7.628-7.981 11.5899-11.0771                                                                            vs                                                     8.105-8.299 10.9084-10.6537                                                                            m                                                      16.395-16.673                                                                              5.4066-5.3172                                                                              m                                                      19.052-19.414                                                                              4.6580-4.5721                                                                              w                                                      20.744-20.871                                                                              4.2819-4.2560                                                                              m                                                      ______________________________________                                    

(d) All of the MnAPSO-36 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XX-D below:

                  TABLE XX-D                                                       ______________________________________                                         2Θ      d, (Å)  I/Io × 100                                     ______________________________________                                         7.132         12.3939     5                                                    7.596         11.6382     21                                                   7.628-7.981   11.5899-11.0771                                                                            100                                                  8.105-8.299   10.9084-10.6537                                                                            33-37                                                13.517-13.778 6.5503-6.4270                                                                               5-17                                                15.797-15.928 5.6099-5.5640                                                                              10-11                                                16.395-16.673 5.4066-5.3172                                                                              31-32                                                19.052-19.414 4.6580-4.5721                                                                              14-17                                                20.744-20.871 4.2819-4.2560                                                                              20-35                                                21.230        4.1848      4                                                    21.655        4.1037      16                                                   21.863-21.986 4.0651-4.0427                                                                               8-14                                                22.119-22.470 4.0186-3.9566                                                                              15                                                   22.713-23.408 3.9150-3.8001                                                                               5-11                                                23.854-23.965 3.7301-3.7131                                                                              5-6                                                  27.219-27.518 3.2761-3.2412                                                                              15-16                                                27.868-27.939 3.2014-3.1934                                                                              2-3                                                  28.252        3.1587      6                                                    28.304-28.536 3.1530-3.1279                                                                              6-8                                                  29.003-29.268 3.0786-3.0513                                                                              6-7                                                  29.347        3.0433      5                                                    30.144-30.230 2.9646-2.9564                                                                              4                                                    30.291-30.526 2.9505-2.9284                                                                              4                                                    31.983-32.094 2.7982-2.7888                                                                              6-9                                                  34.640-34.968 2.5894-2.5659                                                                              7                                                    ______________________________________                                    

EXAMPLE 76D

(a) MnAPSO-44, as prepared in example 64D was subjected to x-ray analysis. The MnAPSO-44 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         9.4           9.39    100                                                      13.0          6.83    20                                                       13.7          6.45    4                                                        16.1          5.52    43                                                       17.3          5.12    5                                                        19.0          4.68    7                                                        20.7          4.29    84                                                       21.7          4.09    21                                                       22.6          3.94    8                                                        23.1          3.86    9                                                        24.4          3.65    58                                                       26.1          3.409   22                                                       27.8          3.205   10                                                       29.7          3.012   5                                                        30.1          2.969   16                                                       30.8          2.900   50                                                       32.5          2.753   4                                                        32.9          2.721   6                                                        34.8          2.577   3                                                        35.5          2.528   9                                                        38.5          2.336   2                                                        39.2          2.299   2                                                        40.0          2.255   2                                                        42.2          2.143   3                                                        42.5          2.125   3                                                        43.6          2.076   2                                                        47.3          1.922   2                                                        48.2          1.890   7                                                        48.7          1.870   4                                                        50.3          1.814   7                                                        53.9          1.701   6                                                        ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-44 of part (a) was calcined in air at 500° C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         9.6           9.21    100                                                      13.1          6.79    26                                                       14.2          6.26    3                                                        16.2          5.46    12                                                       18.0          4.93    18                                                       19.3          4.60    3                                                        20.9          4.25    28                                                       22.3          3.99    3                                                        23.4          3.80    3                                                        25.3          3.526   13                                                       26.3          3.387   9                                                        28.5          3.137   3                                                        28.6          3.123   4                                                        29.9          2.990   2                                                        30.0          2.976   2                                                        30.6          2.921   3                                                        31.1          2.875   7                                                        31.8          2.811   2                                                        32.1          2.791   2                                                        35.1          2.560   3                                                        ______________________________________                                    

(c) The species denominated herein as MnAPSO-44 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being with the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-44 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI-D as follows:

                  TABLE XXI-D                                                      ______________________________________                                         2Θ     d, (Å) Relative Intensity                                     ______________________________________                                         9.420-9.498  9.3883-9.3110                                                                             vs                                                     16.062-16.131                                                                               5.5179-5.4944                                                                             m                                                      20.715-20.790                                                                               4.2877-4.2725                                                                             s                                                      24.396-24.424                                                                               3.6485-3.6444                                                                             m                                                      26.143-26.184                                                                               3.4085-3.4032                                                                             m                                                      30.833-30.853                                                                               2.8999-2.8981                                                                             m                                                      ______________________________________                                    

(d) All of the MnAPSO-44 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXII-D below:

                  TABLE XXII-D                                                     ______________________________________                                         2Θ     d, (Å) I/Io × 100                                       ______________________________________                                         9.420-9.498  9.3883-9.3110                                                                             100                                                    12.930-12.958                                                                               6.8468-6.8318                                                                             20                                                     13.738       6.4458     4                                                      16.062-16.131                                                                               5.5179-5.4944                                                                             43                                                     17.329-17.396                                                                               5.1173-5.0975                                                                             5                                                      18.950-18.998                                                                               4.6828-4.6713                                                                             7                                                      20.715-20.790                                                                               4.2877-4.2725                                                                             84                                                     21.709-21.743                                                                               4.0937-4.0873                                                                             21                                                     22.366-22.583                                                                               3.9748-3.9372                                                                             8                                                      23.061-23.101                                                                               3.8566-3.8501                                                                             9                                                      24.396-24.424                                                                               3.6485-3.6444                                                                             58                                                     26.143-26.184                                                                               3.4085-3.4032                                                                             22                                                     27.837-27.881                                                                               3.2049-3.1999                                                                             10                                                     29.661       3.0117     5                                                      30.002-30.096                                                                               2.9783-2.9692                                                                             16                                                     30.833-20.853                                                                               2.8999-2.8981                                                                             50                                                     32.520-32.562                                                                               2.7532-2.7498                                                                             4                                                      32.900-32.918                                                                               2.7223-2.7208                                                                             6                                                      34.812       2.5770     3                                                      35.516-35.534                                                                               2.5275-2.5263                                                                             9                                                      38.536       2.3361     2                                                      38.185       2.2989     2                                                      39.991       2.2545     2                                                      42.162-42.177                                                                               2.1432-2.1425                                                                             3                                                      42.533-42.541                                                                               2.1254-2.1250                                                                             3                                                      43.607-73.621                                                                               2.0755-2.0749                                                                             2                                                      47.283       1.9224     2                                                      48.157-48.177                                                                               1.8895-1.8888                                                                             7                                                      48.640-48.697                                                                               1.8719-1.8698                                                                             4                                                      50.303-50.307                                                                               1.8138-1.8137                                                                             7                                                      53.885-53.887                                                                               1.7014-1.7013                                                                             6                                                      ______________________________________                                    

EXAMPLE 77D

(a) MnAPSO-47, as prepared in example 49D was subjected to x-ray analysis. The MnAPSO-47 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         4.8           18.44   1                                                        9.4           9.38    100                                                      12.9          6.89    5                                                        13.9          6.40    3                                                        16.0          5.56    9                                                        17.5          5.06    4                                                        18.9          4.69    3                                                        20.5          4.32    30                                                       21.8          4.08    4                                                        22.4          3.98    1                                                        22.9          3.88    3                                                        24.6          3.61    11                                                       25.9          3.445   7                                                        27.6          3.234   2                                                        27.9          3.199   1                                                        29.5          3.033   2                                                        30.5          2.930   10                                                       30.8          2.901   7                                                        31.5          2.845   1                                                        33.2          2.700   1                                                        34.4          2.604   2                                                        34.8          2.576   1                                                        35.7          2.516   2                                                        38.4          2.343   1                                                        39.2          2.297   1                                                        39.6          2.277   1                                                        42.4          2.132   1                                                        43.3          2.091   1                                                        47.6          1.911   1                                                        48.6          1.874   5                                                        50.3          1.813   2                                                        53.2          1.722   1                                                        54.0          1.698   1                                                        ______________________________________                                    

(b) A portion of the as-synthesized MnAPSO-47 of part (a) was calcined in air at 500° C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2Θ      d, (Å)                                                                             I/Io × 100                                         ______________________________________                                         5.0           17.80   1                                                        9.7           9.12    100                                                      10.0          8.85    1                                                        13.1          6.75    5                                                        14.2          6.23    1                                                        16.3          5.45    2                                                        18.0          4.92    2                                                        19.4          4.58    3                                                        20.9          4.24    7                                                        22.4          3.98    1                                                        23.4          3.80    1                                                        25.3          3.521   2                                                        26.3          3.385   2                                                        28.1          3.176   1                                                        28.6          3.125   1                                                        30.0          2.977   1                                                        31.1          2.876   3                                                        31.5          2.837   2                                                        33.9          2.645   1                                                        35.0          2.562   1                                                        49.6          1.838   1                                                        ______________________________________                                    

(c) The species denominated herein as MnAPSO-47 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-47 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-D as follows:

                  TABLE XXIII-D                                                    ______________________________________                                         2Θ     d, (Å) Relative Intensity                                     ______________________________________                                         9.434-9.696  9.3746-9.1214                                                                             vs                                                     15.946-16.276                                                                               5.5579-5.4457                                                                             vw                                                     20.539-20.940                                                                               4.3242-4.2423                                                                             vw-m                                                   24.643       3.6125     w                                                      30.511       2.9297     w                                                      30.820-31.096                                                                               2.9011-2.8759                                                                             vw                                                     ______________________________________                                    

(d) All of the MnAPSO-47 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXIV-D below:

                  TABLE XXIV-D                                                     ______________________________________                                         2Θ      d, (Å)  I/Io × 100                                     ______________________________________                                         4.793-4.964   18.4368-17.8028                                                                            1                                                    9.434-9.696   9.3746-9.1214                                                                              100                                                  12.847-13.107 6.8907-6.7543                                                                              5                                                    13.840-14.211 6.3983-6.2321                                                                              1-3                                                  15.946-16.276 5.5579-5.4457                                                                              2-9                                                  17.544-18.032 5.0550-4.9191                                                                              2-4                                                  18.941-19.365 4.6851-4.5836                                                                              3                                                    20.539-20.940 4.3242-4.2423                                                                               6-30                                                21.811        4.0747      4                                                    22.351-22.352 3.9775-3.9774                                                                              1                                                    22.936        3.8773      3                                                    23.401        3.8013      1                                                    24.643        3.6125      11                                                   25.294-25.864 3.5210      2-7                                                  26.327-27.577 3.3851-3.2344                                                                              2                                                    27.881-28.093 3.1992-3.1762                                                                              1                                                    28.560        3.1253      1                                                    29.448-30.019 3.0331-2.9767                                                                              1-2                                                  30.511        2.9297      10                                                   30.820-31.096 2.9011-2.8759                                                                              3-7                                                  31.448-31.532 2.8446-2.8372                                                                              1-2                                                  33.186-33.894 2.6995-2.6447                                                                              1                                                    34.444        2.6037      2                                                    34.834-35.026 2.5755-2.5618                                                                              1                                                    35.685        2.5159      2                                                    38.412        2.3434      1                                                    39.223        2.2968      1                                                    39.582        2.2768      1                                                    42.403        2.1316      1                                                    43.278        2.0905      1                                                    47.595        1.9105      1                                                    48.584-49.595 1.8739-1.8380                                                                              1-5                                                  50.327        1.8130      2                                                    53.205        1.7215      1                                                    54.006        1.6979      1                                                    ______________________________________                                    

EXAMPLE 78D

The catalytic activity of MnAPSO compositions, calcined samples of the MnAPSO products of Examples 11D, 21D, 25D, 31D, 49D, 55D, 59D and 64D were tested for catalytic cracking.

The catalytic activity was determined using a reactor comprising a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test MnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the MnAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium- n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the MnAPSO compositions. The k_(A) value (cm³ /g min) obtained for the MnAPSO compositions are set forth, below, in Table XXV-D:

                  TABLE XXV-D                                                      ______________________________________                                                       Prepared in                                                                               Rate                                                  MnAPSO        Example No.:                                                                              Constant (k.sub.A)*                                   ______________________________________                                         MnAPSO-5      31D        0.2                                                   MnAPSO-11     25D        0.6                                                   MnAPSO-20     46D        0.2                                                   MnAPSO-31     55D        1.0; 0.5                                              MnAPSO-34     11D        3.1                                                   MnAPSO-35     21D          0.1**                                               MnAPSO-36     59D        0.3                                                   MnAPSO-44     64D        1.5                                                   MnAPSO-47     49D        1.7                                                   ______________________________________                                          *Prior to determination of the catalystic activity of a given MnAPSO, eac      was calcined as follows: (a)MnAPSO5 was calcined at 500° C. in air      for 2 hours; (b)MnAPSO11, MnAPSO34 and MnAPSO36 were calcined in situ;         (c)MnAPSO31 was calcined in air at 500° C. for 1.5 hours and then       at 600° C. for 1 hours; (d)MnAPSO35 was calcined at 500° C.      in nitrogen for 1 hour; and (e)MnAPSO20, MnAPSO44 and MnAPSO47 were            calcined at 500° C. in air for 1 hour.                                  **Less than 0.1                                                          

TITANIUM-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES

Molecular sieves containing titanium, aluminum, phosphorus and silicon as framework tetrahedral oxides are prepared as follows:

PREPARATIVE REAGENTS

In the following examples the TiAPSO compositions were prepared using numerous regents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) Tiipro: titanium isopropoxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

(g) Pr₃ NH: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH); and

(j) C-hex: cyclohexylamine.

PREPARATIVE PROCEDURES

The following preparative examples were carried out by forming a starting reaction mixture by adding the H₃ PO₄ and the water. This mixture was mixed and to this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.

The titanium isopropoxide was added to the above mixture and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. When the organic templating agent was quinuclidine the procedure was modified such that the quinuclidine was dissolved in about one half the water and accordingly the H₃ PO₄ was mixed with about one half the water. (The pH of the mixture was measured and adjusted for temperature). The mixture was than placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for a time or placed in lined screw top bottles for digestion at 100° C. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture. H₃ PO₄ and titanium isopropoxide are given respectively in terms of the P₂ O₅ and TiO₂ content of the reaction mixture.

All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

EXAMPLES 1E TO 30E

TiAPSO molecular sieves were prepared according to the above described preparative procedure and the TiAPSO products determined by x-ray analysis. The results of examples 1E to 30E are set forth in Tables I-E and II-E.

                  TABLE I-E                                                        ______________________________________                                                          Temp    Time                                                  Example                                                                               Template.sup.1                                                                           (°C.)                                                                           (days)                                                                               TiAPSO Product(s).sup.2                         ______________________________________                                         1E     Quin      150     28    TiAPSO-16                                       2E     Quin      200     10    TiAPSO-35; TiAPSO-16                            3E     Quin      200     28    TiAPSO-35; TiAPSO-16                            4E     Quin      225      5    TiAPSO-16                                       5E     Pr.sub.3 N                                                                               150      3    TiAPSO-5                                        6E     Pr.sub.3 N                                                                               150     11    TiAPSO-5                                        7E     Pr.sub.3 N                                                                               200      3    TiAPSO-5                                        8E     Pr.sub.3 N                                                                               200     11    TiAPSO-5                                        9E     Pr.sub.3 N                                                                               100      3     --                                             10E    Pr.sub.3 N                                                                               100     11     --                                             ______________________________________                                          .sup.1 Reaction mixture comprised: 1.0 R: 0.2 TiO.sub.2 : 0.9 Al.sub.2         O.sub.3 : 0.9 P.sub.2 O.sub.5 : 0.2 SiO.sub.2 : 50 H.sub.2 O where "R" is      the organic template.                                                          .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predomenance in the product. The              "--"denotes that TiAPSO products were not identified by Xray analysis.   

                  TABLE II-E                                                       ______________________________________                                                          Temp    Time                                                  Example                                                                               Template.sup.1                                                                           (°C.)                                                                           (days)                                                                               TiAPSO Product(s).sup.2                         ______________________________________                                         11E    C-hex     225      5    TiAPSO-44; TiAPSO-35                            12E    Pr.sub.2 NH                                                                              150      4    TiAPSO-11; TiAPSO-41                            13E    Pr.sub.2 NH                                                                              150     11    TiAPSO-11                                       14E    Pr.sub.2 NH                                                                              200      4    TiAPSO-11                                       15E    Pr.sub.2 NH                                                                              200     11    TiAPSO-11                                       16E    Pr.sub.2 NH                                                                              100      4     --                                             17E    Pr.sub.2 NH                                                                              100     11     --                                             18E    TEAOH     150      4    TiAPSO-34; TiAPSO-5                             19E    TEAOH     150     10    TiAPSO-34; TiAPSO-5                             20E    TEAOH     200      4    TiAPSO-5; TiAPSO-34                             21E    TEAOH     200     10    TiAPSO-5; TiAPSO-34                             22E    TEAOH     100     17     --                                             23E    TEAOH     150      2    TiAPSO-34; TiAPSO-5                             24E    TEAOH     150     13    TiAPSO-34                                       25E    TEAOH     200      2    TiAPSO-34; TiAPSO-5                             26E    TEAOH     200     13    TiAPSO-34                                       27E    MQuin     150     21     --                                             28E    MQuin     200     21    TiAPSO-35                                       29E    MQuin     150     45    TiAPSO-35                                       30E    MQuin     200     45    TiAPSO-35                                       ______________________________________                                          .sup.1 The reaction mixture generally comprised: kR: 0.2 TiO.sub.2 : 0.9       Al.sub.2 O.sub.3 : p P.sub.2 O.sub.5 : q SiO.sub.2 : 50 H.sub.2 O where R      is the organic template; "k" is 1.0 for examples 11E to 22E and 27E to 30      and is 1.5 for examples 23E to 26E; "p" is 0.9 for examples 12E-30E and i      1.0 for example 11E; and "q" is 0.6 for examples 11E and 23E-26E and is        0.2 for examples 12E-22E and 27E-30E.                                          .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predomenance in the product. The "--"         denotes that TiAPSO products were not identified by Xray analysis.       

EXAMPLE 31E

Samples of the products of examples 4E, 6E, 15E, 24E and 30E were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the TiAPSO was prepared being given in parenthesis after the designation of the TiAPSO species.

(a) The chemical analysis for TiAPSO-16 (Example 4E) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.1                                                             P.sub.2 O.sub.5                                                                              36.1                                                             TiO.sub.2     6.8                                                              SiO.sub.2     6.7                                                              Carbon        12.0                                                             Nitrogen      1.9                                                              LOI*          22.9                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.085 TiO₂ : 0.266 Al₂ O₃ : 0.254 P₂ O₅ : 0.112 SiO₂ : and a formula (anhydrous basis) of:

    0.14R(Ti.sub.0.07 Al.sub.0.43 P.sub.0.41 Si.sub.0.09)O.sub.2

(b) The chemical analysis for TiAPSO-35 (Example 30E) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             23.4                                                             P.sub.2 O.sub.5                                                                              28.3                                                             TiO.sub.2     17.6                                                             SiO.sub.2     4.37                                                             Carbon        11.3                                                             Nitrogen      1.6                                                              LOI*          26.3                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.220 TiO₂ : 0.230 Al₂ O₃ : 0.199 P₂ O₅ : 0.073 SiO₂ : and a formula (anhydrous basis) of:

    0.12R(Ti.sub.0.19 Al.sub.0.40 P.sub.0.35 Si.sub.0.06)O.sub.2

(c) The chemical analysis for TiAPSO-5 (Example 6E) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             34.0                                                             P.sub.2 O.sub.5                                                                              46.9                                                             TiO.sub.2     3.0                                                              SiO.sub.2     1.2                                                              Carbon        5.8                                                              Nitrogen      0.74                                                             LOI*          14.4                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.038 TiO₂ : 0.334 Al₂ O₃ : 0.330 P₂ O₅ : 0.020 SiO₂ : and a formula (anhydrous basis) of:

    0.054R(Ti.sub.0.03 Al.sub.0.48 P.sub.0.48 Si.sub.0.01)O.sub.2

(d) The chemical analysis of TiAPSO-11 (Example 15E) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             35.8                                                             P.sub.2 O.sub.5                                                                              49.0                                                             TiO.sub.2     1.08                                                             SiO.sub.2     3.3                                                              Carbon        5.0                                                              Nitrogen      1.0                                                              LOI*          10.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.014 TiO₂ : 0.351 Al₂ O₃ : 0.345 P₂ O₅ : 0.055 SiO₂ : and a formula (anhydrous basis) of:

    0.07R(Ti.sub.0.01 Al.sub.0.48 P.sub.0.47 Si.sub.0.04)O.sub.2

(e) The chemical analysis for TiAPSO-34 (example 24E) was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             32.3                                                             P.sub.2 O.sub.5                                                                              37.9                                                             TiO.sub.2     0.4                                                              SiO.sub.2     8.2                                                              Carbon        9.8                                                              Nitrogen      1.6                                                              LOI*          20.5                                                             ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.01 TiO₂ : 0.32 Al₂ O₃ : 0.27 P₂ O₅ : 0.14 SiO₂ : and a formula (anhydrous basis) of:

    0.103R(Ti.sub.0.01 Al.sub.0.48 P.sub.0.41 Si.sub.0.11)O.sub.2

EXAMPLE 32E

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of example 4E, 11E, 12E, and 21E. Analysis of crystals having a morphology characteristic of TiAPSO compositions gave the following analysis based on relative peak heights:

(a) TiAPSO-44/35 (Example 11E):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Ti        0.02                                                                 Al        0.97                                                                 P         0.94                                                                 Si        0.25                                                                 ______________________________________                                    

(b) TiAPSO-16 (Example 4E):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Ti        0.38                                                                 Al        0.79                                                                 P         0.84                                                                 Si        0.33                                                                 ______________________________________                                    

(c) TiAPSO-34/5 (Example 21E):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Ti         0.005                                                               Al        0.85                                                                 P         1.00                                                                 Si        0.08                                                                 ______________________________________                                    

(d) TiAPSO-11 (Example 12E):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Ti        0.12                                                                 Al        0.88                                                                 P         0.84                                                                 Si        0.07                                                                 ______________________________________                                    

EXAMPLE 33E

Samples of the TiAPSO products of examples 4E, 13E, and 6E were evaluated for adsorption capacities in the calcined form by calcination in air to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain- Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined TiAPSO products were:

(a) TiAPSO-16 (Example 4E):

    ______________________________________                                                 Kinetic      Pressure Temp    Wt. %*                                   Adsorbate                                                                              Diameter, Å                                                                             (Torr)   (°C.)                                                                           Adsorbed                                 ______________________________________                                         O.sub.2 3.46         102      -183    3.3                                      O.sub.2 3.46         744      -183    12.8**                                   n-hexane                                                                               4.3          95       23.6    7.0                                      H.sub.2 O                                                                              2.65         4.6      23.3    13.4                                     H.sub.2 O                                                                              2.65         19       23.2    25.4                                     ______________________________________                                          *TiAPSO-16 was calcined at 500° C. in air for 1.5 hours prior to        being activated.                                                               **Sample may not have been fully equilibrated.                           

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

(b) TiAPSO-11 (Example 13E):

    ______________________________________                                                   Kinetic     Pressure Temp   Wt. %*                                   Adsorbate Diameter, Å                                                                            (Torr)   (°C.)                                                                          Adsorbed                                 ______________________________________                                         O.sub.2   3.46        101      -183   9.3                                      O.sub.2   3.46        736      -183   10.3                                     neopentane                                                                               5.0         742      23.0   1.1                                      cyclohexane                                                                              6.0         67       22.9   5.2                                      H.sub.2 O 2.65        4.6      22.4   12.4                                     H.sub.2 O 2.65        19       22.5   23.4                                     ______________________________________                                          *TiAPSO-11 was calcined at 600° C. in air for 1.5 hours prior to        being activated.                                                         

The above data demonstrate that the pore size of the calcined product is about 6.0Å.

(c) TiAPSO-5 (Example 6E):

    ______________________________________                                                   Kinetic     Pressure Temp   Wt. %*                                   Adsorbate Diameter, Å                                                                            (Torr)   (°C.)                                                                          Adsorbed                                 ______________________________________                                         O.sub.2   3.46        101      -183   13.0                                     O.sub.2   3.46        736      -183   14.5                                     neopentane                                                                               6.2         742      23.0   4.9                                      cyclohexane                                                                              6.0         67       22.9   7.1                                      H.sub.2 O 2.65        4.6      22.4   14.7                                     H.sub.2 O 2.65        19       22.5   23.4                                     ______________________________________                                          *TiAPSO was calcined at 600° C. in air for 2.5 hours prior to bein      activated.                                                               

The above data demonstrate that the pore size of the calcined product is greater than 6.2Å.

EXAMPLE 34E

(a) TiAPSO-5 compositions, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III below:

                  TABLE III-E                                                      ______________________________________                                         2θ     d, Å  Relative Intensity                                      ______________________________________                                         7.3-7.5      12.11-11.79                                                                              s-vs                                                    19.7-19.9    4.51-4.46 m                                                       20.9-21.0    4.25-4.23 m-s                                                     22.3-22.5    3.99-3.95 m-vs                                                    25.8-26.1    3.453-3.411                                                                              m                                                       28.9-29.1    3.089-3.069                                                                              w-m                                                     ______________________________________                                    

(b) TiAPSO-5 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are X-ray powder diffraction patterns characterized by Table IV-E below.

                  TABLE IV-E                                                       ______________________________________                                         2θ      d,(Å) 100 × I/Io                                       ______________________________________                                         7.3-7.5       12.11-11.79                                                                               94-100                                                12.9-13.0     6.86-6.81 19-22                                                  14.9-15.0     5.95-5.91  9-21                                                  19.7-19.9     4.51-4.46 26-50                                                  20.9-21.0     4.25-4.23 43-82                                                  22.3-2.5      3.99-3.95  60-100                                                24.6-24.8     3.62-3.59 7-9                                                    25.8-26.1     3.453-3.414                                                                              25-40                                                  28.9-29.1     3.089-3.069                                                                              17-27                                                  30.0-30.2     2.979-2.959                                                                              18-25                                                  33.5-33.7     2.675-2.660                                                                              6-9                                                    34.5-34.7     2.600-2.585                                                                              17-19                                                  36.8-37.1     2.442-2.423                                                                              6                                                      37.5-37.8     2.398-2.380                                                                              10-13                                                  41.4-41.5     2.181-2.176                                                                              5-6                                                    41.7-42.0     2.166-2.151                                                                              3-4                                                    42.5-42.9     2.127-2.108                                                                              3-6                                                    43.6-43.7     2.076-2.071                                                                              3--4                                                   44.9-45.0     2.019-2.014                                                                              3--4                                                   47.4-47.6     1.918-1.910                                                                              5-7                                                    47.8-47.9     1.903-1.900                                                                              6-7                                                    51.4-51.5     1.778-1.774                                                                              4-5                                                    51.8-51.9     1.765-1.762                                                                              3-4                                                    55.6          1.653     6                                                      ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-5 of Example 6E was subjected to X-ray analysis. The TiAPSO-5 product was characterized by the x-ray powder diffraction pattern of Table V-E, below:

                  TABLE V-E                                                        ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                         7.3           12.11   94                                                       9.1*          9.72    3                                                        12.9          6.86    19                                                       13.6*         6.51    6                                                        14.9          5.95    21                                                       18.2*         4.87    6                                                        19.7          4.51    50                                                       20.9          4.25    82                                                       22.3          3.99    100                                                      24.6          3.62    9                                                        25.8          3.453   40                                                       28.9          3.089   27                                                       30.0          2.979   25                                                       33.5          2.675   9                                                        34.5          2.600   19                                                       36.8          2.442   6                                                        37.5          2.398   13                                                       41.4          2.181   6                                                        42.0          2.151   4                                                        42.5          2.127   6                                                        43.6          2.076   4                                                        44.9          2.019   3                                                        47.6          1.910   7                                                        51.4          1.778   4                                                        51.8          1.765   4                                                        55.6          1.653   6                                                        ______________________________________                                          *peak may contain an impurity.                                           

(d) The TiAPSO-5 compositions of Example 6E was calcined at 600° C. in air for 2.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table VI-E, below:

                  TABLE VI-E                                                       ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                         7.5           11.79   100                                                      12.5*         7.08    8                                                        13.0          6.81    22                                                       15.0          5.91    9                                                        19.9          4.46    26                                                       21.0          4.23    43                                                       22.5          3.95    60                                                       24.8          3.59    7                                                        26.1          3.414   25                                                       29.1          3.069   17                                                       30.2          2.959   18                                                       33.7          2.660   6                                                        34.7          2.585   17                                                       37.1          2.423   6                                                        37.8          2.380   10                                                       41.7          2.166   3                                                        42.9          2.108   3                                                        47.4          1.918   5                                                        47.9          1.900   6                                                        51.4          1.778   3                                                        51.8          1.765   3                                                        ______________________________________                                          *peak may contain an impurity.                                           

EXAMPLE 35-E

(a) TiAPSO-11, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-E below:

                  TABLE VII-E                                                      ______________________________________                                         2θ     d,(Å)                                                                               Relative Intensity                                       ______________________________________                                         9.4-9.6      9.41-9.21                                                                               vw-m                                                     19.9-20.5    4.46-4.33                                                                               m                                                        21.0-21.8    4.23-4.08                                                                               vs                                                       22.0-22.1    4.04-4.02                                                                               m-vs                                                     22.4-22.6    3.97-3.93                                                                               m-s                                                      22.7         3.92     m                                                        23.1-23.4    3.85-3.80                                                                               m-vs                                                     ______________________________________                                    

(b) The TiAPSO-11 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern of Table VIII-E below:

                  TABLE VIII-E                                                     ______________________________________                                         2θ      d,(Å) 100 × I/Io                                       ______________________________________                                         8.0-8.1       11.05-10.92                                                                              23-59                                                  9.4-9.6       9.41-9.21 sh-73                                                   9.8          9.03      51                                                     12.8-13.2     6.92-6.71 26-27                                                  13.5-13.7     6.56-6.46  9-11                                                  14.7-15.0     6.03-5.91  9-18                                                  15.6-16.1     5.68-5.51 32-63                                                  16.2-16.3     5.47-5.44  7-18                                                  19.0-19.5     4.67-4.55 20-23                                                  19.9-20.5     4.46-4.33 31-68                                                  21.0-21.8     4.23-4.08 100                                                    22.0-22.1     4.04-4.02  57-100                                                22.4-22.6     3.97-3.93 54-82                                                  22.7          3.92      73                                                     23.1-23.4     3.85-3.80 63-91                                                  23.9-24.4     3.72-3.65 23                                                     24.7          3.60      27                                                     26.5-26.6     3.363-3.351                                                                              17-36                                                  27.2-27.3     3.278-3.267                                                                              16-20                                                  27.6-27.7     3.232-3.220                                                                              20-23                                                  27.8-27.9     3.209-3.200                                                                              20-21                                                  28.5-28.6     3.132-3.121                                                                              14-27                                                  28.7          3.110     11-32                                                  29.0-29.5     3.079-3.028                                                                              27-31                                                  29.6-29.7     3.018-3.008                                                                              23-34                                                  30.3-30.4     2.950-2.940                                                                              20-22                                                  31.4-31.6     2.849-2.831                                                                              14-23                                                  32.5-32.9     2.755-2.722                                                                              26-32                                                  33.9-34.2     2.644-2.622                                                                              11-23                                                  35.5-35.6     2.529-2.522                                                                              17-19                                                  36.5          2.462     18                                                     37.2-37.5     2.417- 2.398                                                                             14-23                                                  38.7-39.4     2.327-2.287                                                                              14-17                                                  41.0          2.201     11                                                     42.8          2.113     14                                                     43.6          2.076      9                                                     44.5-44.6     2.036-2.032                                                                               9-14                                                  45.0          2.014     14                                                     48.7-49.2     1.870-18.52                                                                              14                                                     49.4          1.845     11                                                     49.6          1.838     11                                                     50.6          1.804      7-18                                                  53.4          1.716     11                                                     53.6          1.707      9                                                     54.6-54.7     1.681-1.678                                                                               9-14                                                  55.4-55.8     1.658-1.647                                                                              11-14                                                  ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-11 of Example 13E was subjected to x-ray analysis. The TiAPSO-11 product was characterized by the x-ray powder diffraction pattern of Table IX-E, below:

                  TABLE IX-E                                                       ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                         8.1           10.92   59                                                       9.4           9.41    73                                                       13.2          6.71    27                                                       15.0          5.91    18                                                       15.7          5.64    50                                                       16.3          5.44    18                                                       19.0          4.67    23                                                       20.5          4.33    68                                                       21.0          4.23    100                                                      22.1          4.02    73                                                       22.6          3.93    82                                                       22.7          3.92    73                                                       23.2          3.83    91                                                       24.4          3.65    23                                                       24.7          3.60    27                                                       26.5          3.363   36                                                       28.5          3.132   27                                                       28.7          3.110   32                                                       29.0          3.079   27                                                       29.5          3.028   23                                                       31.4          2.849   23                                                       32.9          2.722   32                                                       34.2          2.622   23                                                       36.5          2.462   18                                                       37.5          2.398   23                                                       39.4          2.287   14                                                       42.8          2.113   14                                                       44.6          2.032   14                                                       45.0          2.014   14                                                       48.7          1.870   14                                                       50.6          1.804   18                                                       54.7          1.678   14                                                       55.4          1.658   14                                                       ______________________________________                                    

(d) The TiAPSO-11 composition of Example 13E was calcined at 500° C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table X-E, below:

                  TABLE X-E                                                        ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                         8.1           10.92   23                                                       9.6           9.21    sh                                                       9.8           9.03    51                                                       12.8          6.92    26                                                       13.5          6.56    11                                                       13.7          6.46     9                                                       14.7          6.03     9                                                       16.1          5.51    63                                                       19.5          4.55    20                                                       19.9          4.46    31                                                       21.8          4.08    100                                                      22.1          4.02    57                                                       22.4          3.97    54                                                       23.4          3.80    63                                                       23.9          3.72    23                                                       24.2          3.68    17                                                       26.6          3.351   17                                                       27.2          3.278   20                                                       27.6          3.232   23                                                       27.8          3.209   20                                                       28.5          3.132   14                                                       28.7          3.110   11                                                       29.5          3.028   31                                                       29.7          3.008   34                                                       30.3          2.950   20                                                       31.6          2.831   14                                                       32.5          2.755   26                                                       33.9          2.644   11                                                       35.5          2.529   17                                                       37.2          2.417   14                                                       38.7          2.327   17                                                       41.0          2.201   11                                                       43.6          2.076    9                                                       44.5          2.036    9                                                       49.2          1.852   14                                                       49.4          1.845   11                                                       49.6          1.838   11                                                       53.4          1.716    9                                                       53.6          1.707    9                                                       55.8          1.647   11                                                       ______________________________________                                    

EXAMPLE 36E

(a) TiAPSO-16, as referred to herein in both the as-synthesized and calcined form, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-E below:

                  TABLE XI-E                                                       ______________________________________                                         2θ     d,(Å) Relative Intensity                                      ______________________________________                                         11.4         7.75      m-vs                                                    18.7         4.75      m                                                       21.9-22.1    4.05-4.02 m-vs                                                    26.4-26.5    3.370-3.363                                                                              m                                                       29.6-29.8    3.018-3.002                                                                              m                                                       29.9         2.984     m                                                       30.1         2.971     m                                                       ______________________________________                                    

(b) The TiAPSO-16 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the X-ray powder diffraction pattern of Table XII-E below:

                  TABLE XII-E                                                      ______________________________________                                         2θ      d,(Å) 100 × I/Io                                       ______________________________________                                         10.5          8.41      5                                                      11.4          7.75       72-100                                                18.7          4.75      25-59                                                  21.1          4.21      3                                                      21.9-22.1     4.05-4.02  56-100                                                22.8-22.9     3.90-3.89 10-15                                                  23.3          3.818     3                                                      25.0          3.561     6                                                      25.4-25.5     3.506-3.489                                                                              13-17                                                  26.4-26.5     3.370-3.363                                                                              20-23                                                  26.6          3.346     16                                                     26.9-27.1     3.314-3.290                                                                               4-15                                                  28.9-29.1     3.088-3.073                                                                              12-13                                                  29.6-29.8     3.018-3.002                                                                              22-27                                                  29.9          2.984     24                                                     30.1          2.971     23                                                     32.5-32.7     2.755-2.739                                                                              3-4                                                    34.4-34.8     2.607-2.581                                                                              3-5                                                    37.3-37.6     2.411-2.394                                                                              4-5                                                    37.8-37.9     2.380-2.373                                                                               8-14                                                  38.2-38.4     2.356-2.343                                                                              5                                                      39.5          2.282     3-4                                                    39.7-39.8     2.270-2.265                                                                              3-5                                                    40.1          2.247     7                                                      40.5          2.227     4                                                      44.4          2.040     3                                                      47.8-47.9     1.904-1.899                                                                              5                                                      48.0-48.1     1.897-1.893                                                                              6-8                                                    48.2-48.3     1.887-1.885                                                                              7-8                                                    48.4-48.5     1.881-1.876                                                                              7-8                                                    48.8          1.865     5.6                                                    49.0          1.858     5                                                      49.2          1.853     4                                                      54.2          1.692     3                                                      54.3          1.689     3                                                      ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-16 of example 4E was subjected to x-ray analysis. The TiAPSO-16 product was characterized by the x-ray powder diffraction pattern of Table XIII-E, below:

                  TABLE XIII-E                                                     ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         11.4          7.75    72                                                       18.7          4.74    59                                                       22.1          4.02    100                                                      22.9          3.89    11                                                       25.3          3.521   15                                                       26.4          3.376   13                                                       26.6          3.346   16                                                       26.9          3.314   15                                                       29.1          3.073   13                                                       29.8          3.002   22                                                       29.9          2.984   24                                                       30.1          2.971   23                                                       34.8          2.581   3                                                        37.6          2.395   5                                                        37.9          2.371   14                                                       38.4          2.343   5                                                        39.5          2.282   4                                                        39.7          2.270   5                                                        40.1          2.247   7                                                        40.5          2.227   4                                                        47.8          1.904   5                                                        48.1          1.893   8                                                        48.2          1.887   8                                                        48.5          1.876   8                                                        48.8          1.865   6                                                        49.0          1.858   5                                                        49.2          1.853   4                                                        ______________________________________                                          *peak may contain impurity                                               

(d) The TiAPSO-16 composition of part (c) was calcined at 500° C. in air for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XIV-E, below:

                  TABLE XIV-E                                                      ______________________________________                                         2θ       d,(Å)                                                                              100 × I/Io                                        ______________________________________                                         10.5           8.41    5                                                       11.4           7.75    100                                                     18.7           4.75    25                                                      21.1           4.27    3                                                       21.9           4.05    56                                                      22.8           3.90    10                                                      25.0           3.561   6                                                        25.4*         3.506   14                                                      25.5           3.489   13                                                      26.4           3.370   20                                                      28.9           3.088   12                                                      29.7           3.007   27                                                      34.6           2.594   5                                                       37.6           2.391   5                                                       37.9           2.373   9                                                       38.2           2.356   5                                                       48.0           1.897   6                                                       48.3           1.885   7                                                       ______________________________________                                          *peak may contain impurity                                               

EXAMPLE 37E

(a) TiAPSO-34, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-E below:

                  TABLE XV-E                                                       ______________________________________                                         2θ     d,(Å) Relative Intensity                                      ______________________________________                                         9.4-9.5      9.41-9.31 vs                                                      12.9-13.0    6.86-6.81 w-m                                                     16.0-16.2    5.54-5.47 w-m                                                     20.5-20.8    4.33-4.27 m-vs                                                    30.5-30.9    2.931-2.894                                                                              m                                                       31.5-31.6    2.840-2.831                                                                              vw-m                                                    ______________________________________                                    

(b) The TiAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XVI-E below:

                  TABLE XVI-E                                                      ______________________________________                                         2θ      d,(Å) 100 × I/Io                                       ______________________________________                                         9.4-9.5       9.41-9.31 100                                                    12.9-13.0     6.86-6.81 16-31                                                  14.0-14.1     6.33-6.28  7-16                                                  17.8-17.9     4.98-4.96 16-23                                                  19.2          4.62      10                                                     20.5-20.8     4.33-4.27 38-97                                                  22.1-22.2     4.02-4.00 8-9                                                    23.1-23.3     3.85-3.82  8-14                                                  25.0-25.1     3.562-3.548                                                                              17-27                                                  25.8-26.2     3.453-3.401                                                                              19-21                                                  27.5-27.9     3.243-3.198                                                                               7-10                                                  28.2-28.3     3.164-3.153                                                                               7-12                                                  29.5-29.8     3.028-2.998                                                                               8-12                                                  30.5-30.9     2.931-2.894                                                                              31-39                                                  31.1-31.3     2.876-2.858                                                                              Sh-29                                                  31.5-31.6     2.840-2.831                                                                               8-32                                                  32.3-32.4     2.772-2.763                                                                              6-7                                                    33.2          2.698     5                                                      33.8          2.652     5                                                      34.4-34.9     2.607-2.571                                                                              8-9                                                    35.0          2.564     3                                                      36.1-36.2     2.488-2.481                                                                              6-7                                                    38.8          2.321     3                                                      39.6-39.8     2.276-2.265                                                                              5-7                                                    40.2          2.243     5                                                      43.0          2.103     5                                                      43.4          2.085     7                                                      47.5          1.914     5                                                      48.9-49.2     1.863-1.852                                                                              5-8                                                    49.8          1.831     5                                                      50.9-51.0     1.794-1.791                                                                              7-8                                                    51.5-51.6     1.774-1.771                                                                              3-5                                                    53.1-53.2     1.725-1.722                                                                              7-8                                                    54.4-54.5     1.687-1.684                                                                              5-6                                                    55.8-55.9     1.647-1.645                                                                              6-7                                                    ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-34 of example 24E was subjected to x-ray analysis. The TiAPSO-34 product was characterized by the x-ray powder diffraction pattern of Table XVII-E below:

                  TABLE XVII-E                                                     ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                          9.4          9.41    100                                                      12.9          6.86    16                                                       14.0          6.33    16                                                       16.0          5.54    50                                                       17.9          4.96    23                                                       20.5          4.33    97                                                       22.1          4.02    8                                                        23.1          3.85    8                                                        25.1          3.548   27                                                       25.8          3.453   21                                                       27.5          3.243   7                                                        28.3          3.153   7                                                        29.5          3.028   8                                                        30.5          2.931   39                                                       31.1          2.876   29                                                       31.6          2.831   8                                                        32.4          2.763   7                                                        33.2          2.698   5                                                        33.8          2.652   5                                                        34.4          2.607   8                                                        35.0          2.564   3                                                        36.2          2.481   7                                                        38.8          2.321   3                                                        39.6          2.276   7                                                        43.0          2.103   5                                                        43.4          2.085   7                                                        47.5          1.914   5                                                        48.9          1.863   8                                                        49.8          1.831   5                                                        50.9          1.794   7                                                        51.6          1.771   3                                                        53.1          1.725   7                                                        54.4          1.687   5                                                        55.8          1.647   7                                                        ______________________________________                                    

(d) The TiAPSO-34 compositions of example 24E was calcined at 500° C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XVIII-E, below:

                  TABLE XVIII-E                                                    ______________________________________                                         2θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                          9.5          9.31    100                                                      13.0          6.81    31                                                       14.1          6.28     7                                                       16.2          5.47    19                                                       17.9          4.96    16                                                       19.2          4.62    10                                                       20.8          4.27    38                                                       22.2          4.00     9                                                       23.3          3.82    14                                                       25.0          3.562   17                                                       26.2          3.401   19                                                       27.9          3.198   10                                                       28.2          3.164   12                                                       29.8          2.998   12                                                       30.9          2.894   31                                                       31.3          2.858   sh                                                       32.4          2.763    9                                                       34.9          2.571    9                                                       36.2          2.481    7                                                       39.8          2.265    5                                                       40.2          2.243    5                                                       49.2          1.852    5                                                       51.0          1.791    7                                                       ______________________________________                                    

EXAMPLE 38E

(a) TiAPSO-35, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-E below:

                  TABLE XIX-E                                                      ______________________________________                                         2Θ    d, (Å)                                                                               Relative Intensity                                       ______________________________________                                         10.9-11.1   8.12-7.97 m                                                        13.3-13.7   6.66-6.46 m                                                        17.3-17.4   5.13-5.10 w-m                                                      20.8-21.1   4.27-4.21 m                                                        21.9-22.2   4.06-4.00 m-vs                                                     28.3-28.7   3.153-3.110                                                                              m                                                        ______________________________________                                    

(b) The TiAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XX-E below:

                  TABLE XX-E                                                       ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.6-8.8       10.28-10.05                                                                              13-14                                                  10.9-11.1     8.12-7.97 36-74                                                  13.3-13.7     6.66-6.46 20-39                                                  15.9-16.1     5.57-5.51 11-15                                                  17.3-17.4     5.13-5.10 17-75                                                  17.6-17.7     5.04-5.01 13-17                                                  20.8-21.1     4.27-4.21 25-49                                                  21.9-22.2     4.06-4.00 65-100                                                 23.2-23.7     3.83-3.75 22-32                                                  24.9-25.2     3.58-3.534                                                                               19-30                                                  26.6-26.9     3.363-3.314                                                                              19-35                                                  28.3-28.7     3.153-3.110                                                                              30-48                                                  29.1-29.2     3.069-3.058                                                                              11-15                                                  29.6-29.7     3.018-3.008                                                                               6-39                                                  31.5-31.7     2.840-2.823                                                                               9-11                                                  32.1-32.7     2.788-2.739                                                                              30-41                                                  34.3-34.6     2.614-2.592                                                                              11-17                                                  35.0-35.1     2.564-2.557                                                                              4-5                                                    35.8-35.9     2.508-2.501                                                                              5-6                                                    37.8-38.0     2.380-2.368                                                                               9-13                                                  39.5          2.281     4-5                                                    40.9          2.206     3-4                                                    41.9          2.156     6                                                      42.1-42.6     2.146-2.122                                                                              5-6                                                    42.7          2.118     4-6                                                    48.4-48.5     1.881-1.877                                                                               9-13                                                  49.0          1.859     5-6                                                    50.1          1.821     10-11                                                  55.0-55.1     1.670-1.667                                                                               9-13                                                  55.4-55.5     1.658-1.656                                                                               9-10                                                  ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-35 of example 30E was subjected to x-ray analysis. The TiAPSO-35 product was characterized by the x-ray powder diffraction pattern of Table XXI-E below:

                  TABLE XXI-E                                                      ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.6           10.28   13                                                       10.9          8.12    36                                                       11.4*         7.76    6                                                        13.3          6.66    21                                                       15.9          5.57    11                                                       17.3          5.13    75                                                       17.7          5.01    13                                                       18.6*         4.77    6                                                        20.8          4.27    49                                                       21.9          4.06    100                                                      22.6*         3.93    9                                                        23.2          3.83    32                                                       24.9          3.58    19                                                       25.2*         3.534   28                                                       26.9          3.314   19                                                       28.3          3.153   47                                                       29.1          3.069   11                                                       29.7          3.008   6                                                        31.5          2.840   9                                                        32.1          2.788   38                                                       34.3          2.614   11                                                       35.0          2.564   4                                                        35.9          2.501   6                                                        37.8          2.380   9                                                        39.5          2.281   4                                                        40.9          2.206   4                                                        41.9          2.156   6                                                        42.6          2.122   6                                                        42.7          2.118   6                                                        44.7*         2.027   6                                                        47.6*         1.910   11                                                       48.4          1.881   9                                                        49.0          1.859   6                                                        49.6*         1.838   7                                                        50.1          1.821   11                                                       54.0*         1.698   6                                                        55.0          1.670   9                                                        55.4          1.658   9                                                        ______________________________________                                          *peak may contain an impurity                                            

(d) The calcined TiAPSO-35 compositions of example 2E was calcined at 600° C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XXII-E, below.

                  TABLE XXII-E                                                     ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.8           10.05   13                                                       11.1          7.97    74                                                       11.5*         7.69    100                                                      13.7          6.46    39                                                       17.6          5.04    17                                                       18.9*         4.70    26                                                       21.1          4.21    26                                                       22.2          4.00    65                                                       23.1*         3.85    26                                                       23.7          3.75    22                                                       25.2          3.534   30                                                       26.6          3.363   35                                                       27.4*         3.255   26                                                       28.7          3.110   35                                                       29.6*         3.018   39                                                       29.8*         2.998   44                                                       32.7          2.739   30                                                       34.6          2.592   17                                                       38.0          2.368   13                                                       48.5          1.877   13                                                       55.1          1.667   13                                                       ______________________________________                                          *peak may contain an impurity                                            

EXAMPLE 39E

(a) TiAPSO-44, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-E below:

                  TABLE XIX-E                                                      ______________________________________                                         2Θ    d, (Å)                                                                             Relative Intensity                                         ______________________________________                                         9.5         9.30    s                                                          16.1        5.49    m                                                          20.8        4.27    vs                                                         22.0        4.05    m                                                          24.5        3.63    m                                                          30.9        2.893   m                                                          ______________________________________                                    

(b) The TiAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XXIV-E below:

                  TABLE XXIV-E                                                     ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         9.5           9.30    83                                                       11.0          8.06    45                                                       13.0          6.79    24                                                       13.4          6.62    30                                                       13.9          6.40     3                                                       16.1          5.49    51                                                       17.4          5.11    48                                                       19.0          4.66     5                                                       20.8          4.27    100                                                      21.1          4.22    36                                                       22.0          4.05    77                                                       22.7          3.92     7                                                       23.2          3.83    19                                                       24.5          3.63    52                                                       26.2          3.400   20                                                       27.0          3.307   11                                                       27.9          3.195   10                                                       28.6          3.123   28                                                       29.8          3.000    6                                                       30.3          2.954   14                                                       30.9          2.893   57                                                       31.7          2.820    6                                                       32.2          2.777   30                                                       32.6          2.745    5                                                       33.1          2.708    4                                                       35.0          2.567    4                                                       35.7          2.519   11                                                       38.7          2.328    3                                                       42.1          2.145    4                                                       42.6          2.122    5                                                       43.7          2.073    4                                                       47.4          1.920    3                                                       48.2          1.888   12                                                       48.8          1.867    8                                                       51.5          1.775    6                                                       54.1          1.696    7                                                       ______________________________________                                    

(c) A portion of the as-synthesized TiAPSO-44 of Example 11E was subjected to X-ray analysis. The TiAPSO-44 product was characterized by the x-ray powder diffraction pattern of Table XXV-E, below:

                  TABLE XXV-E                                                      ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.7*          10.21   14                                                       9.5           9.30    83                                                       11.0          8.06    45                                                       11.7*         7.57    3                                                        13.0          6.79    24                                                       13.4          6.62    30                                                       13.9          6.40    3                                                        16.1          5.49    51                                                       17.4          5.11    48                                                       17.8*         4.98    7                                                        19.0          4.66    5                                                        20.8          4.27    100                                                      21.1          4.22    36                                                       21.5*         4.13    19                                                       22.0          4.05    77                                                       22.7          3.92    7                                                        23.2          3.83    19                                                       23.6*         3.78    3                                                        24.5          3.63    52                                                       25.1*         3.554   8                                                        25.4*         3.501   4                                                        25.6*         3.481   3                                                        26.2          3.400   20                                                       27.0          3.307   11                                                       27.9          3.195   10                                                       28.6          3.123   28                                                       29.2*         3.062   5                                                        29.8          3.000   6                                                        30.3          2.954   14                                                       30.9          2.893   57                                                       31.7          2.820   6                                                        32.2          2.777   30                                                       32.6          2.745   5                                                        33.1          2.708   4                                                        34.6*         2.595   7                                                        35.0          2.567   4                                                        35.1*         2.559   3                                                        35.7          2.519   11                                                       37.9*         2.372   3                                                        38.7          2.328   3                                                        42.1          2.145   4                                                        42.4*         2.134   5                                                        42.6          2.122   5                                                        43.0*         2.103   6                                                        43.7          2.073   4                                                        47.4          1.920   3                                                        48.2          1.888   12                                                       48.7*         1.871   8                                                        48.8          1.867   8                                                        49.7*         1.836   4                                                        50.4*         1.809   9                                                        51.5          1.775   6                                                        54.1          1.696   7                                                        ______________________________________                                          *peak may contain an impurity                                            

EXAMPLE 40E

In order to demonstrate the catalytic activity of the TiAPSO compositions, calcined samples of the TiAPSO products of Examples 6E, 13E, and 24E were tested for catalytic cracking of n-butane.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test TiAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The TiAPSO samples were calcined in air (TiAPSO-5 at 600° C. for 2.5 hours; TiAPSO-11 at 600° C. for 1.5 hours; and TiAPSO-34 at 500° C. for 2 hours) to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromotography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the TiAPSO compositions. The k_(A) value (cm³ /g min) obtained for the TiAPSO compositions are set forth, below, in Table XXVI-E:

                  TABLE XXVI-E                                                     ______________________________________                                                TiAPSO          k.sub.A                                                 ______________________________________                                                TiAPSO-5        0.6                                                            TiAPSO-11       0.5                                                            TiAPSO-34       1.3                                                     ______________________________________                                    

ZINC-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES

Molecular sieves containing zinc, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

PREPARATIVE REAGENTS

In the following examples the ZnAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) ZnAc: Zinc Acetate, Zn(C₂ H₃ O₂)₂ ·4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;

(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH₃)₄ NOH·5H₂ O;

(i) TPAOH: 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C₃ H₇)₄ NOH;

(j) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(k) Pr₃ N: Tri-n-propylamine, (C₃ H₇)₃ N;

(l) Quin: Quinuclidine, (C₇ H₁₃ N);

(m) C-hex: cyclohexylamine; and

(n) DEEA: diethylethanolamine, (C₂ H₅)₂ NC₂ H₅ OH.

PREPARATIVE PROCEDURE

The ZnAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:

    eR:fZnO:gAl.sub.2 O.sub.3 :hP.sub.2 O.sub.5 :iSiO.sub.2 2:jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅), SiO₂ and H₂ O, respectively. The values for e, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples where "j" was 50 in each example, and "e" was 1.0.

The reaction mixtures were prepared by forming a starting reaction mixture comprising the H₃ PO₄ and a portion of the water. This mixture was stirred and the aluminum source added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The zinc source (zinc acetate) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

EXAMPLES 1F TO 41F

ZnAPSO molecular sieves were prepared according to the above described procedure and the ZnAPSO products determined by x-ray analysis. The results of preparative examples 1F to 41F are set forth in Tables I-F and II-F. The reactive zinc source was zinc acetate. The reactive aluminum source was Alipro. The reactive phosphorus source was H₃ PO₄. the reactive silicon source was LUDOX-LS. The organic templating agents are set forth in Tables I-F and II-F.

                                      TABLE I-F                                    __________________________________________________________________________     Example.sup.2                                                                       Template                                                                            f g h i Temp (°C.)                                                                    Time (hrs)                                                                           ZnAPSO Product(s).sup.1                          __________________________________________________________________________     1F   Pr.sub.3 N                                                                          0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              150    42   ZnAPSO-36; ZnAPSO-5                              2F   Pr.sub.3 N                                                                          0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              150   183   ZnAPSO-36; ZnAPSO-5                              3F   Pr.sub.3 N                                                                          0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              200    42   ZnAPSO-5; ZnAPSO-36                              4F   Pr.sub.3 N                                                                          0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              200   183   ZnAPSO-5; ZnAPSO-36                              5F   Pr.sub.3 N                                                                          0.2                                                                              0.9                                                                              0.9                                                                              0.2                                                                              150    48   ZnAPSO-5; ZnAPSO-36                              6F   TPAOH                                                                               0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              200   165   ZnAPSO-5;                                        7F   TPAOH                                                                               0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              200   165   ZnAPSO-5                                         8F   Pr.sub.2 N                                                                          0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              150    42   ZnAPSO-46; ZnAPSO-39                                                           ZnAPSO-11                                        9F   Pr.sub.2 NH                                                                         0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              150   183   ZnAPSO-39; ZnAPSO-11                                                           ZnAPSO-46                                        10F  Pr.sub.2 NH                                                                         0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              200    42   ZnAPSO-11; ZnAPSO-46                                                           ZnAPSO-39                                        11F  Pr.sub.2 NH                                                                         0.1                                                                              1.0                                                                              1.0                                                                              0.6                                                                              200   183   ZnAPSO-11; ZnAPSO-39                                                           ZnASPO-46                                        12F  Pr.sub.2 NH                                                                         0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              150    41   ZnAPSO-46; ZnAPSO-31                             13F  Pr.sub.2 NH                                                                         0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              150   145   ZnAPSO-31; ZnAPSO-46                             14F  Pr.sub.2 NH                                                                         0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              200    41   ZnAPSO-31                                        15F  Pr.sub.2 NH                                                                         0.2                                                                              0.9                                                                              0.7                                                                              0.6                                                                              200   145   ZnAPSO-31                                        __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predominance in the product                   .sup.2 AlPO.sub.4 -31 (as described in U.S. Pat. No. 4,310,440) employed       as seed crystals in examples 12F to 15F.                                 

                                      TABLE II-F                                   __________________________________________________________________________     Example                                                                             Template                                                                             f g  h i Temp (°C.)                                                                    Time (hrs)                                                                           ZnAPSO Product(s).sup.1                        __________________________________________________________________________     16F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              100   134   ZnAPSO-34                                      17F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              100   251   ZnAPSO-34                                      18F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              150   134   ZnAPSO-5; ZnAPSO-34                            19F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              150   251   ZnAPSO-34; Znapso-5                            20F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              200   134   ZnAPSO-5; ZnAPSO-34                            21F  TEAOH 0.1                                                                              1.0                                                                               1.0                                                                              0.6                                                                              200   251   ZnAPSO-34; ZnAPSO-5                            22F  TEAOH 0.1                                                                              0.95                                                                              0.7                                                                              0.6                                                                              100    17   ZnAPSO-34                                      23F  TEAOH 0.1                                                                              0.95                                                                              0.7                                                                              0.6                                                                              100    66   ZnAPSO-34                                      24F  TEAOH 0.1                                                                              0.95                                                                              0.7                                                                              0.6                                                                              100   166   ZnAPSO-34                                      25F  TEAOH 0.1                                                                              0.95                                                                              0.7                                                                              0.6                                                                              100    66   ZnAPSO-34                                      26F  TMAOH 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150    46   ZnAPSO-20; ZnAPSO-43                           27F  TMAOH 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150   165   ZnAPSO-20; ZnAPSO-43                           28F  TMAOH 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200    46   ZnAPSO-20; ZnAPSO-43                           29F  TMAOH 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200   165   ZnAPSO-20; ZnAPSO-43                           30F  QUIN  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150    40   ZnAPSO-35                                      31F  Quin  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150   158   ZnAPSO-35                                      32F  Quin  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200    40   ZnAPSO-35                                      33F  Quin  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200   158   ZnAPSO-35                                      34F  C-hex 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150    40   ZnAPSO-44                                      35F  C-hex 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150   158   ZnAPSO-44                                      36F  C-hex 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200    40   ZnAPSO-44; ZnAPSO-5                            37F  C-hex 0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200   158   ZnAPSO-44; ZnAPSO-5                            38F  DEEA  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150    40   ZnAPSO-47; ZnAPSO-5                            39F  DEEA  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              150   158   ZnAPSO-47; ZnAPSO-5                            40F  DEEA  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200    40   ZnAPSO-47; ZnAPSO-5                            41F  DEEA  0.2                                                                              0.9                                                                               0.7                                                                              0.6                                                                              200   158   ZnAPSO-47                                      __________________________________________________________________________      .sup.1 Major species as identified by xray powder diffraction pattern of       product, except that when two or more species were identified the species      are listed in the order of their predomenance in the product.            

EXAMPLE 42F

Samples of the products of examples 4F, 17F, 24F, 33F, 35F and 39F were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the ZnAPSO was prepared being given in parenthesis after the designation of the ZnAPSO species.

(a) The chemical analysis for ZnAPSO-5 (Example 4F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            31.3                                                              P.sub.2 O.sub.5                                                                             45.7                                                              ZnO          2.8                                                               SiO.sub.2    5.7                                                               Carbon       5.5                                                               LOI*         12.8                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.17R; 0.11 ZnO; 1.0 Al₂ O₃ ; 1.05 P₂ O₅ ; 0.31 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R (Zn.sub.0.03 Al.sub.0.44 P.sub.0.47 Si.sub.0.07)O.sub.2

(b) The chemical analysis for ZnAPSO-34 (Example 17F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            32.3                                                              P.sub.2 O.sub.5                                                                             35.3                                                              ZnO          2.8                                                               SiO.sub.2    1.6                                                               Carbon       5.0                                                               LOI*         26.7                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.16 R; 0.11 ZnO; 1.0 Al₂ O₃ ; 0.79 P₂ O₅ : 0.08 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R (Zn.sub.0.03 Al.sub.0.54 P.sub.0.41 Si.sub.0.02)O.sub.2

(c) The chemical analysis for ZnAPSO-34 (Example 24F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            36.2                                                              P.sub.2 O.sub.5                                                                             30.3                                                              ZnO          3.8                                                               SiO.sub.2    3.7                                                               Carbon       5.2                                                               LOI*         24.0                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.15R; 0.13 ZnO; 1.0 Al₂ O₃ ; 0.60 P₂ O₅ : 0.07 SiO₂ ; and a formula (anhydrous basis) of:

    0.04R (Zn.sub.0.04 Al.sub.0.57 P.sub.0.34 Si.sub.0.05)O.sub.2

(d) The chemical analysis of ZnAPSO-35 (Example 33F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            30.4                                                              P.sub.2 O.sub.5                                                                             33.2                                                              ZnO          5.6                                                               SiO.sub.2    7.6                                                               Carbon       10.1                                                              LOI*         22.1                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.40R; 0.23 ZnO; 1.0 Al₂ O₃ ; 0.78 P₂ O₅ ; 0.42 SiO₂ ; and a formula (anhydrous basis) of:

    0.12R (Zn.sub.0.06 Al.sub.0.47 P.sub.0.37 Si.sub.0.10)O.sub.2

(e) The chemical analysis for ZnAPSO-44 (Example 35F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            27.5                                                              P.sub.2 O.sub.5                                                                             31.1                                                              ZnO          4.8                                                               SiO.sub.2    10.6                                                              Carbon       11.7                                                              LOI*         25.1                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.60R; 0.22 ZnO; 1.0 Al₂ O₃ ; 0.81 P₂ O₅ ; 0.65 SiO₂ ; and a formula (anhydrous basis) of:

    0.13R (Zn.sub.0.05 Al.sub.0.44 P.sub.0.36 Si.sub.0.15)O.sub.2

(f) The chemical analysis of ZnAPSO-47 (Example 39F) was:

    ______________________________________                                         Component    Weight Percent                                                    ______________________________________                                         Al.sub.2 O.sub.3                                                                            30.4                                                              P.sub.2 O.sub.5                                                                             32.6                                                              ZnO          5.3                                                               SiO.sub.2    6.5                                                               Carbon       7.7                                                               LOI*         23.4                                                              ______________________________________                                          *LOI = Loss on Ignition                                                  

The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.35R; 0.22 ZnO; 1.0 Al₂ O₃ ; 0.77 P₂ O₅ ; 0.36 SiO₂ ; and a formula (anhydrous basis) of:

    0.09R (Zn.sub.0.05 Al.sub.0.49 P.sub.0.37 Si.sub.0.09)O.sub.2

EXAMPLE 43F

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of examples 4F, 24F, 33F, 35F and 39F. Analysis of crystals having a morphology characteristic of the ZnAPSO products gave the following analysis based on relative peak heights:

(a) ZnAPSO-5 (Example 4F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         1                                                                   Al        44                                                                   P         50                                                                   Si         5                                                                   ______________________________________                                    

(b) ZnAPSO-34 (Example 24F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         3                                                                   Al        45                                                                   P         46                                                                   Si         6                                                                   ______________________________________                                    

(c) ZnAPSO-35 (Example 33F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         5                                                                   Al        43                                                                   P         46                                                                   Si         6                                                                   ______________________________________                                    

(d) ZnAPSO-36 (Example 4F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         4                                                                   Al        42                                                                   P         50                                                                   Si         4                                                                   ______________________________________                                    

(e) ZnAPSO-44 (Example 35F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         2                                                                   Al        43                                                                   P         39                                                                   Si        16                                                                   ______________________________________                                    

(f) ZnAPSO-47 (Example 39F):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Zn         5                                                                   Al        42                                                                   P         44                                                                   Si         9                                                                   ______________________________________                                    

EXAMPLE 44F

Samples of the ZnAPSO products of examples 4F, 27F, 33F, 35F and 39F were for adsorption capacities evaluated in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined ZnAPSO products were:

(a) ZnAPSO-5 (Example 4F):

    ______________________________________                                                  Kinetic    Pressure Temp    Wt. %                                     Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                 ______________________________________                                         O.sub.2  3.46       99       -183    11.0                                      O.sub.2  3.46       749      -183    14.9                                      neopentane                                                                              6.2        100      23.4    3.5                                       cyclohexane                                                                             6.0        57       23.4    7.4                                       H.sub.2 O                                                                               2.65       4.6      23.2    13.5                                      H.sub.2 O                                                                               2.65       16.8     23.5    17.5                                      ______________________________________                                          *calcined in air at 500° C. for 0.75 hours and at 600° C.        for 1.25 hours prior to activation.                                      

The above data demonstrate that the pore size of the calcined product is greater than 6.2 Å.

(b) ZnAPSO-34 (Example 27F):

    ______________________________________                                                 Kinetic    Pressure Temp    Wt. %                                      Adsorbate                                                                              Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                  ______________________________________                                         O.sub.2 3.46       99       -183    14.5                                       O.sub.2 3.46       725      -183    25.8                                       isobutane                                                                              5.0        100      22.8    0.8                                        n-hexane                                                                               4.3        98       23.3    13.3                                       H.sub.2 O                                                                              2.65       4.6      23.1    19.9                                       H.sub.2 O                                                                              2.65       17.8     23.1    30.1                                       ______________________________________                                          *calcined in air at 500° C. for 2 hours prior to activation       

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

(c) ZnAPSO-35 (Example 33F):

    ______________________________________                                                 Kinetic    Pressure Temp    Wt. %                                      Adsorbate                                                                              Diameter, Å                                                                           (Torr)   (°C.)                                                                           Adsorbed*                                  ______________________________________                                         O.sub.2 3.46       99       -183    10.2                                       O.sub.2 3.46       725      -183    19.1                                       n-hexane                                                                               4.3        98       23.3    8.6                                        isobutane                                                                              5.0        100      22.8    0.8                                        H.sub.2 O                                                                              2.65       4.6      23.1    17.2                                       H.sub.2 O                                                                              2.65       17.8     23.1    26.3                                       ______________________________________                                          *calcined in air at 500° C. for 1.75 hours prior to activation    

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

(d) ZnAPSO-44 (Example 35F):

    ______________________________________                                                  Kinetic    Pressure  Temp  Wt. %                                      Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2  3.46        99       -183  10.3                                       O.sub.2  3.46       745       -183  19.8                                       n-hexane 4.3         98       23.3   9.7                                       isobutane                                                                               5.0        100       22.8   0.8                                       H.sub.2 O                                                                               2.65        4.6      23.1  14.0                                       H.sub.2 O                                                                               2.65       17.8      23.1  24.0                                       ______________________________________                                          *calcined in air at 500° C. for 67 hours prior to activation      

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

(e) ZnAPSO-47 (Example 39F):

    ______________________________________                                                  Kinetic    Pressure  Temp  Wt. %                                      Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                         Adsorbed*                                  ______________________________________                                         O.sub.2  3.46        99       -183  13.9                                       O.sub.2  3.46       725       -183  23.0                                       isobutane                                                                               5.0        100       23.8   0.7                                       n-hexane 4.3         98       23.3   7.8                                       H.sub.2 O                                                                               2.65        4.6      23.1  18.8                                       H.sub.2 O                                                                               2.65       17.8      23.1  27.0                                       ______________________________________                                          *calcined in air at 500° C. for 1.75 hours prior to activation    

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

EXAMPLE 45F

(a) ZnAPSO-5, as prepared in example 4F, was subjected to x-ray analysis. ZnAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.4           11.91   100                                                      7.9**         11.17   29                                                      12.85          6.88    10                                                      13.5*          6.56    1                                                       14.85          5.96    19                                                      15.85**        5.60    3                                                       16.45**        5.39    8                                                       19.1**         4.65    9                                                       19.7           4.51    38                                                      20.3**         4.38    4                                                       20.8**         4.27    10                                                      21.05          4.22    30                                                      21.5**         4.14    5                                                       21.65**        4.10    5                                                       22.4           3.973   73                                                      22.95**        3.876   3                                                       23.85**        3.730   1                                                       24.75          3.596   2                                                       25.9           3.442   25                                                      27.2**         3.279   4                                                       27.75**        3.212   1                                                       28.3**         3.154   2                                                       29.0           3.078   15                                                      29.95          2.981   15                                                      30.35**        2.947   2                                                       32.0**         2.798   3                                                       33.6           2.666   4                                                       34.45          2.602   12                                                      34.8**         2.577   4                                                       35.45**        2.532   2                                                       35.9           2.501   1                                                       36.95          2.434   3                                                       37.7           2.386   7                                                       41.45*         2.177   2                                                       42.2           2.141   3                                                       42.8           2.112   1                                                       43.4           2.085   1                                                       45.0           2.013   1                                                       47.6           1.910   4                                                       51.4           1.778   2                                                       51.95          1.760   1                                                       55.6*          1.654   2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized ZnAPSO-5 of part (a) was calcined in air at 500° C. for about 0.75 hours and then in air at 600° C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          7.45          11.91   100                                                      7.85*         11.23   21                                                       8.2*          10.79   7                                                       12.9           6.87    20                                                      13.45*         6.57    3                                                       14.9           5.95    6                                                       16.5*          5.37    5                                                       19.35*         4.58    5                                                       19.75          4.49    24                                                      20.3           4.38    10                                                      20.7           4.29    4                                                       21.1           4.21    28                                                      21.4           4.14    11                                                      22.4           3.962   69                                                      22.75*         3.907   5                                                       24.85          3.584   2                                                       26.0           3.430   24                                                      27.25*         3.275   4                                                       27.45*         3.252   2                                                       27.8*          3.207   2                                                       28.15*         3.168   3                                                       28.35*         3.146   2                                                       29.1           3.068   16                                                      30.1           2.970   14                                                      33.7           2.658   3                                                       34.6           2.592   13                                                      35.45*         2.532   4                                                       37.05          2.427   3                                                       37.85          2.378   6                                                       42.4           2.132   2                                                       47.8           1.903   2                                                       51.5           1.774   3                                                       55.8           1.647   1                                                       ______________________________________                                          *Impurity Peak                                                           

(c) The ZnAPSO-5 compositions are generally characterized by the data of Table III-F below.

                  TABLE III-F                                                      ______________________________________                                         2θ     d (Å) Relative Intensity                                      ______________________________________                                         7.2-7.4      12.28-11.91                                                                              vs                                                      19.4-19.8    4.58-4.48 m                                                       21.0-21.2    4.23-4.19 m                                                       22.3-22.5    3.971-3.952                                                                              m-s                                                     25.7-26.0    3.466-3.427                                                                              w-m                                                     ______________________________________                                    

(d) The ZnAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table IV-F, below.

                  TABLE IV-F                                                       ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         7.2-7.4       12.28-11.91                                                                              100                                                    12.6-13.0     7.03-6.81  8-21                                                  14.6-14.9     6.07-5.95  9-20                                                  19.4-19.8     4.58-4.48 24-38                                                  21.0-21.2     4.23-4.19 20-35                                                  22.3-22.5     3.971-3.952                                                                              47-82                                                  24.7-24.9     3.604-3.576                                                                              1-2                                                    25.7-26.0     3.466-3.427                                                                              18-27                                                  28.9-29.1     3.089-3.069                                                                              10-20                                                  29.9-30.1     2.988-2.969                                                                              12-17                                                  33.6-33.8     2.667-2.652                                                                              3-4                                                    34.4-34.6     2.607-2.592                                                                              10-14                                                  36.9-37.0     2.436-2.430                                                                              2-3                                                    37.6-37.9     2.392-2.374                                                                              5-8                                                    41.45         2.177     0-2                                                    42.2-42.4     2.141-2.132                                                                              2-3                                                    42.8          2.113     0-1                                                    43.4          2.090     0-1                                                    45.0          2.014     0-1                                                    47.5-47.8     1.914-1.903                                                                              2-4                                                    51.3-51.6     1.781     2-3                                                    51.95         1.760     0-1                                                    55.5-55.8     1.656-1.647                                                                              0-2                                                    ______________________________________                                    

EXAMPLE 46F

(a) ZnAPSO-11, as prepared in example 10F was subjected to x-ray analysis. ZnAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          6.6**         13.44   10                                                       7.7**         11.46   97                                                       8.1           10.89   26                                                       8.45**        10.44   6                                                        9.45*         9.35    60                                                      13.3*          6.66    22                                                      13.8**         6.43    4                                                       14.9**         5.94    5                                                       15.3**         5.80    8                                                       15.7           5.64    24                                                      16.2           5.47    3                                                       16.65**        5.33    7                                                       18.35**        4.83    16                                                      19.0           4.66    4                                                       19.8**         4.49    4                                                       20.45*         4.35    29                                                      21.1*          4.20    100                                                     21.55**        4.123   24                                                      22.2*          4.008   32                                                      22.75          3.905   85                                                      23.2           3.830   45                                                      24.2**         3.674   5                                                       24.45**        3.643   3                                                       24.8           3.590   5                                                       26.55          3.355   14                                                      26.8*          3.327   12                                                      27.8**         3.212   4                                                       28.7*          3.109   20                                                      29.05*         3.075   5                                                       29.8*          3.000   11                                                      30.15*         2.966   11                                                      30.75**        2.909   3                                                       31.1**         2.874   5                                                       31.6           2.832   6                                                       32.85*         2.725   11                                                      34.3*          2.615   7                                                       34.5**         2.598   5                                                       35.9*          2.501   6                                                       36.55*         2.459   5                                                       37.85*         2.377   10                                                      39.7*          2.270   1                                                       43.0*          2.103   4                                                       44.85          2.022   3                                                       48.85*         1.864   3                                                       50.8           1.797   1                                                       54.8           1.675   1                                                       ______________________________________                                          *Peak may contain impurity                                                     **Impurity Peak                                                          

(b) The ZnAPSO-11 compositions are generally characterized by the data of Table V-F below.

                  TABLE V-F                                                        ______________________________________                                         2θ     d (Å) Relative Intensity                                      ______________________________________                                         9.35-9.45    9.44-9.35 m                                                       13.15-13.35  6.67-6.63 m                                                        21.1-21.25  4.21-4.19 s-vs                                                    22.75-22.85  3.911-3.896                                                                              s-vs                                                    23.15-23.3   3.839-3.819                                                                              w-m                                                     26.8-26.9    3.327-3.313                                                                              w-m                                                     ______________________________________                                    

(c) The ZnAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VI-F, below:

                  TABLE VI-F                                                       ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         8.05-8.1       10.98-10.92                                                                               8-26                                                 9.35-9.45      9.44-9.35 54-72                                                 13.15-13.35    6.67-6.63 22-40                                                 15.65-15.75    5.66-5.62 10-27                                                 16.05-16.2     5.53-5.47 0-3                                                   19.0           4.66      0-4                                                   19.85          4.49-4.46  4-14                                                 20.4-20.5      4.35-4.33 19-38                                                  21.1-21.25    4.21-4.19  83-100                                                22.1-22.25    4.018-3.998                                                                              12-32                                                 22.75-22.85    3.911-3.896                                                                               85-100                                               23.15-23.3     3.839-3.819                                                                              12-45                                                 26.45-26.55    3.369-3.354                                                                               8-14                                                 26.8-26.9      3.327-3.313                                                                              12-40                                                 28.7-28.8      3.111-3.100                                                                              20-36                                                 29.75-29.85    3.005-2.993                                                                              11-23                                                 31.6-31.8      2.832-2.813                                                                               0-10                                                  32.8-32.95    2.731-2.719                                                                               7-15                                                 34.2-34.3      2.620-2.615                                                                              6-9                                                   35.85-36.0     2.503-2.495                                                                               6-12                                                 36.45-36.55    2.464-2.459                                                                              4-8                                                   37.65-37.7     2.389-2.387                                                                              0-7                                                   37.85          2.377      0-10                                                 39.7           2.271     0-1                                                    43.0-43.05    2.103-2.100                                                                              0-4                                                   44.85-44.9     2.022-2.018                                                                              0-3                                                   48.75-48.85    1.867-1.864                                                                              0-3                                                   50.8-50.9      1.797-1.794                                                                              0-3                                                   54.8           1.675     0-1                                                   ______________________________________                                    

EXAMPLE 47F

(a) ZnAPSO-20, as prepared in example 29F, was subjected to x-ray analysis. ZnAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         12.35*         7.17    6                                                       13.9           6.37    47                                                      14.35*         6.16    2                                                       14.5*          6.10    1                                                       14.65*         6.04    1                                                       14.85*         5.96    1                                                       19.75          4.50    40                                                      20.8*          4.27    1                                                       21.05*         4.22    1                                                       21.7*          4.09    3                                                       22.1           4.024   2                                                       24.25          3.672   100                                                     24.85*         3.582   1                                                       27.0*          3.302   5                                                       28.05          3.181   12                                                      28.65*         3.116   1                                                       31.45          2.845   12                                                      32.45*         2.758   1                                                       34.55          2.596   20                                                      37.45          2.402   2                                                       38.4*          2.248   1                                                       40.1           2.344   4                                                       42.65          2.121   4                                                       45.13*         2.009   1                                                       47.4           1.917   5                                                       49.35*         1.846   1                                                       51.8           1.765   9                                                       ______________________________________                                          *Impurity peak                                                           

(b) The ZnAPSO-20 compositions are generally characterized by the data of Table VII-F below:

                  TABLE VII-F                                                      ______________________________________                                         2θ      d, (Å)                                                                               Relative Intensity                                     ______________________________________                                         13.85-14.0    6.39-6.33 m                                                      19.65-19.8    4.52-4.48 m                                                      24.15-24.3    3.685-3.663                                                                              vs                                                      28.0-28.15   3.187-3.170                                                                              w                                                      31.35-31.5    2.853-2.840                                                                              w                                                       34.5-34.65   2.600-2.589                                                                              w-m                                                    ______________________________________                                    

(c) The ZnAPSO-20 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VIII-F, below:

                  TABLE VIII-F                                                     ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         13.85-14.0     6.39-6.33 45-47                                                 19.65-19.8     4.52-4.48 40-41                                                  22.0-22.15    4.040-4.013                                                                              2-3                                                   24.15-24.3     3.685-3.663                                                                              100                                                    28.0-28.15    3.187-3.170                                                                              12-13                                                 31.35-31.5     2.853-2.840                                                                              11-12                                                  34.5-34.65    2.600-2.589                                                                              16-20                                                 37.35-37.5     2.408-2.398                                                                               2                                                     40.0-40.2     2.254-2.243                                                                               4                                                    42.55-42.7     2.125-2.118                                                                               4                                                    47.35-47.5     1.920-1.914                                                                               5                                                    51.75-51.9     1.767-1.762                                                                              8-9                                                   ______________________________________                                    

EXAMPLE 48F

(a) ZnAPSO-31, as prepared in example 14F, was subjected to x-ray analysis. ZnAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                          6.6**         13.40   14                                                       7.7**         11.45   10                                                       8.1**         10.94   11                                                       8.5           10.40   50                                                       9.5*          9.32    8                                                        9.85*         8.96    2                                                       12.45**        7.12    25                                                      13.4           6.60    10                                                      17.05          5.21    5                                                       17.4**         5.10    3                                                       18.25          4.86    8                                                       20.3           4.38    52                                                      21.3*          4.17    16                                                      21.6**         4.11    10                                                      22.0           4.036   30                                                      22.6           3.394   100                                                     23.55*         3.779   2                                                       24.25**        3.668   3                                                       25.15*         3.543   4                                                       27.0**         3.302   3                                                       27.75*         3.213   12                                                      27.95          3.192   13                                                      28.2*          3.162   4                                                       28.7**         3.109   3                                                       29.75          3.004   10                                                      30.3           2.950   4                                                       31.75          2.810   20                                                      32.95          2.718   4                                                       34.2**         2.623   3                                                       35.15          2.554   12                                                      35.7*          2.515   3                                                       35.9*          2.500   3                                                       36.2           2.481   4                                                       37.25*         2.413   3                                                       37.65*         2.390   2                                                       38.25          2.353   3                                                       39.3           2.291   2                                                       40.3           2.238   2                                                       45.0*          2.014   2                                                       46.6           1.949   4                                                       47.4**         1.918   2                                                       48.6           1.873   2                                                       51.5           1.774   7                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The ZnAPSO-31 compositions are generally characterized by the data of Table IX-F below:

                  TABLE IX-F                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         8.4-8.5      10.53-10.40                                                                              m                                                       20.2-20.3    4.40-4.37 m                                                       21.3         4.171     w                                                       22.0         4.036     m                                                       22.5-22.6    3.952-3.934                                                                              vs                                                       31.6-31.75  2.831-2.820                                                                              w-m                                                     ______________________________________                                    

(c) The ZnAPSO-31 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table X-F, below:

                  TABLE X-F                                                        ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         8.4-8.5        10.53-10.40                                                                              50-53                                                 9.45-9.5       9.35-9.32 7-8                                                   13.2-13.4      6.76-6.60 10-11                                                  18.2-18.25    4.87-4.86 5-8                                                   20.2-20.3      4.39-4.37 49-52                                                 21.3           4.171     16-18                                                 22.0           4.036      30                                                   22.5-22.6      3.952-3.934                                                                              100                                                   26.9-27.0      3.314-3.302                                                                              3-7                                                   27.95-28.25    3.192-3.529                                                                              13-17                                                 29.6-29.7      3.018-3.008                                                                               8-10                                                 30.2-30.3      2.959-2.950                                                                              0-4                                                    31.6-31.75    2.831-2.820                                                                              18-20                                                  32.95         2.718     4-9                                                   35.15-35.2     2.554-2.550                                                                               12                                                   36.1-36.2      2.489-2.481                                                                              4-7                                                   37.25-37.35    2.413-2.409                                                                              2-3                                                    38.25         2.353      3                                                    39.3           2.291      2                                                    40.3           2.238      2                                                     46.6-46.65    1.949-1.948                                                                              4-6                                                    47.4-47.45    1.918-1.916                                                                              2-4                                                   51.5           1.774      7                                                    ______________________________________                                    

EXAMPLE 49F

(a) ZnAPSO-34, as prepared in example 24F, was subjected to x-ray analysis. ZnAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

                  TABLE XIII-F                                                     ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         9.6            9.19    100                                                     12.95          6.84    16                                                      14.2           6.25    14                                                      16.1           5.50    42                                                      18.1           4.90    22                                                      20.65          4.30    91                                                      22.4           3.978   5                                                       23.15          3.842   5                                                       25.3           3.521   25                                                      25.9           3.437   18                                                      27.7           3.218   5                                                       28.45          3.135   6                                                       29.65          3.015   5                                                       30.6           2.920   33                                                      31.3           2.856   23                                                      32.5           2.755   2                                                       34.45          2.602   7                                                       36.4           2.468   5                                                       38.8           2.320   4                                                       39.75          2.267   5                                                       43.15          2.097   4                                                       43.55*         2.077   4                                                       47.65          1.908   5                                                       49.10          1.856   8                                                       49.9           1.827   4                                                       51.0           1.791   4                                                       53.15          1.723   3                                                       54.65          1.679   3                                                       55.9           1.645   3                                                       ______________________________________                                          *impurity peak                                                           

(b) A portion of the as-synthesized ZnAPSO-34 of part (a) was calcined in air at 500° C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ       d, (Å)                                                                             100 × I/Io                                        ______________________________________                                         9.55           9.27    100                                                     12.95          6.85    24                                                      16.15          5.49    13                                                      17.95          4.94    10                                                      20.75          4.28    30                                                      22.2           4.004   2                                                       23.25          3.828   5                                                       25.2           3.533   9                                                       26.15          3.411   12                                                      28.45          3.138   4                                                       30.9           2.896   16                                                      31.35          2.852   9                                                       ______________________________________                                    

(c) The ZnAPSO-34 compositions are generally characterized by the data of Table XI-F below.

                  TABLE XI-F                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.4-9.8      9.41-9.03 m-vs                                                    12.7-13.2    6.97-6.71 w-m                                                     15.8-16.2    5.61-5.47 w-m                                                     20.5-20.9    4.33-4.25 m-vs                                                    25.0-25.3    3.562-3.520                                                                              vw-m                                                    30.5-30.9    2.931-2.894                                                                              w-m                                                     ______________________________________                                    

(d) The ZnAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-F, below:

                  TABLE XII-F                                                      ______________________________________                                         2θ       d, (Å)                                                                               100 × I/Io                                      ______________________________________                                         9.4-9.8        9.41-9.03  77-100                                               12.7-13.2      6.97-6.71 16-31                                                 14.0-14.3      6.33-6.19  0-22                                                 15.8-16.2      5.61-5.47 16-47                                                 17.8-18.2      4.98-4.87 13-29                                                 20.5-20.9      4.33-4.25  36-100                                               22.2-22.5      4.004-3.952                                                                              5.8                                                   23.0-23.3      3.867-3.818                                                                              5-6                                                   25.0-25.3      3.562-3.520                                                                               9-32                                                  25.7-26.25    3.466-3.395                                                                              12-20                                                 27.45-27.7     3.249-3.220                                                                              5-8                                                    28.1-28.45    3.175-3.137                                                                              4-8                                                   29.4-29.8      3.038-2.998                                                                              0-5                                                   30.5-30.9      2.931-2.894                                                                              16-35                                                  31.0-31.65    2.885-2.827                                                                               9-25                                                 32.2-32.5      2.780-2.755                                                                              0-2                                                   34.3-34.8      2.614-2.578                                                                              5-8                                                   36.1-36.4      2.488-2.468                                                                              0-5                                                   38.65-38.8     2.330-2.321                                                                              0-4                                                   39.5-39.8      2.281-2.265                                                                              4-7                                                   43.0-43.4      2.103-2.085                                                                              4                                                     47.5-48.0      1.914-1.895                                                                              3-6                                                   48.8-49.1      1.866-1.855                                                                               8-10                                                 49.9           1.859     0-4                                                   50.8-51.0      1.797-1.791                                                                              0-4                                                    53.1-53.15    1.725-1.723                                                                              0-3                                                   54.5-54.8      1.684-1.675                                                                              0-3                                                   55.8-55.9      1.647-1.645                                                                              0-4                                                   ______________________________________                                    

EXAMPLE 50F

(a) ZnAPSO-35, as prepared in example 33F, was subjected to x-ray analysis. ZnAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.6           10.27   20                                                       10.5*         8.44    sh                                                       10.95         8.08    47                                                       11.35         7.80    4                                                        13.30         6.66    39                                                       15.9          5.57    10                                                       17.3          5.13    72                                                       17.8          4.98    sh                                                       21.15         4.20    48                                                       21.9          4.06    100                                                      23.15         3.841   19                                                       23.65         3.762   3                                                        25.05         3.552   4                                                        26.8          3.325   22                                                       28.7          3.107   30                                                       29.1          3.069   sh                                                       32.1          2.788   43                                                       34.75         2.582   9                                                        35.5          2.530   3                                                        35.8          2.507   5                                                        37.75         2.382   5                                                        39.35         2.889   4                                                        42.35         2.134   6                                                        43.15         2.096   4                                                        48.6          1.873   11                                                       49.4          1.845   8                                                        51.55         1.773   6                                                        55.3          1.661   6                                                        ______________________________________                                          *impurity peak                                                           

(b) A portion of the as-synthesized ZnAPSO-35 of part (a) was calcined in air at 500° C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.45*         11.85   10                                                       8.7           10.15   22                                                       11.0          8.04    91                                                       13.5          6.55    100                                                      17.45         5.08    35                                                       21.0          4.23    21                                                       22.15         4.011   60                                                       23.5          3.782   19                                                       25.15         3.542   13                                                       27.2          3.278   20                                                       28.6          3.122   28                                                       29.35         3.041   14                                                       32.45         2.759   28                                                       ______________________________________                                          *impurity peak                                                           

(c) The ZnAPSO-35 compositions obtained to date have patterns which are generally characterized by the data of Table XIII-F below.

                  TABLE XIII-F                                                     ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         10.8-11.0    8.19-8.04 m-vs                                                    13.30-13.5   6.66-6.56 m-vs                                                     17.2-17.45  5.16-5.08 m                                                       20.95-21.2   4.24-4.19 m                                                        21.9-22.15  4.06-4.01 m-vs                                                    32.0-32.5    2.797-2.755                                                                              m                                                       ______________________________________                                    

(d) The ZnAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-F below:

    ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.6-8.7       10.27-10.16                                                                              18-22                                                  10.8-11.0     8.19-8.04 43-91                                                  11.35         7.80      0-4                                                    13.30-13.5    6.66-6.56  39-100                                                15.8-15.9     5.61-5.57  0-10                                                   17.2-17.45   5.16-5.08 35-75                                                  17.8-17.9     4.98-4.96  0-sh                                                  20.95-21.2    4.24-4.19 21-49                                                   21.9-22.15   4.06-4.01  60-100                                                23.0-23.5     3.867-3.786                                                                               0-19                                                  23.65         3.762     0-3                                                    24.85-25.15   3.583-3.541                                                                               4-13                                                  26.6-27.2     3.351-3.278                                                                              20-22                                                  28.5-28.8     3.132-3.100                                                                              26-30                                                   29.1-29.35   3.069-3.043                                                                              sh-14                                                  32.0-32.5     2.797-2.755                                                                              28-43                                                  34.55-34.9    2.596-2.571                                                                              0-9                                                    35.7-35.8     2.515-2.507                                                                              0-5                                                    37.75         2.382     0-5                                                    39.35         2.889     0-4                                                     42.1-42.35   2.146-2.134                                                                              0-6                                                    43.0-43.2     2.103-2.094                                                                              0-4                                                    48.5-48.7     1.877-1.870                                                                               0-11                                                  49.35-49.4    1.847-1.845                                                                              0-8                                                    51.4-51.6     1.778-1.771                                                                              0-7                                                    55.3-55.4     1.661-1.658                                                                              0-6                                                    ______________________________________                                    

EXAMPLE 51F

(a) ZnAPSO-36, as prepared in example 1F, was subjected to x-ray analysis. ZnAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.45**        11.85   76                                                       7.95          11.13   100                                                      8.2           10.76   sh                                                       12.9**        6.87    3                                                        13.6          6.52    4                                                        14.9**        5.95    10                                                       15.9          5.58    10                                                       16.45         5.38    25                                                       19.1          4.64    16                                                       19.75**       4.50    15                                                       20.8*         4.27    32                                                       21.05**       4.22    sh                                                       21.75         4.09    14                                                       22.1          4.025   14                                                       22.4*         3.966   24                                                       23.0          3.863   3                                                        23.95         3.716   5                                                        25.9**        3.440   9                                                        27.3          3.269   11                                                       28.35         3.147   7                                                        29.05*        3.074   9                                                        30.0**        2.978   8                                                        30.35         2.944   4                                                        32.0          2.796   8                                                        33.2          2.698   1                                                        33.65**       2.663   1                                                        34.5**        2.599   6                                                        34.8          2.575   7                                                        35.9          2.500   2                                                        37.75         2.383   2                                                        40.3          2.237   2                                                        41.45         2.178   2                                                        42.2          2.142   1                                                        47.6*         1.910   2                                                        51.35         1.779   2                                                        54.0          1.697   1                                                        55.65         1.652   2                                                        ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The ZnAPSO-36 compositions obtained to date have patterns which are generally characterized by the data of Table XV-F below.

                  TABLE XV-F                                                       ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.45-8.0     11.14-11.04                                                                              vs                                                      16.45-16.5   5.38-5.36 w-m                                                     19.1-19.2    4.65-4.62 w-m                                                     20.8-20.9    4.28-4.25 w-m                                                     21.75-21.8   4.09-4.08 w                                                       22.05-22.15  4.027-4.017                                                                              w                                                       ______________________________________                                    

(c) The ZnAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-F below:

                  TABLE XVI-F                                                      ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         7.45-8.0      11.14-11.04                                                                              100                                                    8.2-8.3       10.76-10.68                                                                               0-sh                                                  13.55-13.6    6.53-6.50 3-4                                                    15.85-15.95   5.60-5.56 10-12                                                  16.45-16.5    5.38-5.36 18-31                                                  19.1-19.2     4.65-4.62 19-22                                                  20.8-20.9     4.28-4.25 17-39                                                  21.75-21.8    4.09-4.08 10-17                                                  22.05-22.15   4.027-4.017                                                                              14-17                                                   23.0-23.05   3.865-3.859                                                                              3-4                                                    23.85-24.0    3.728-3.707                                                                              3-6                                                    27.25-27.35   3.273-3.260                                                                               9-15                                                  28.3-28.4     3.152-3.142                                                                              6-9                                                    30.1-30.4     2.970-2.940                                                                              4-6                                                    31.95-32.1    2.803-2.788                                                                               6-11                                                  33.2-33.6     2.698-2.665                                                                              1-2                                                    34.75-34.9    2.580-2.572                                                                               7-10                                                  35.85-35.95   2.504-2.497                                                                              2-6                                                    37.75-37.8    2.384-2.380                                                                              2                                                      40.15-40.4    2.246-2.232                                                                              1-3                                                    41.45-41.5    2.180-2.176                                                                              1-2                                                    42.2-42.3     2.142-2.137                                                                              0-2                                                     51.4-51.45   1.779-1.776                                                                              2                                                      54.0          1.697     0-1                                                    55.4-55.8     1.658-1.648                                                                              1-2                                                    ______________________________________                                    

EXAMPLE 52F

(a) ZnAPSO-39, as referred to in example 9F, was subjected to x-ray analysis. ZnAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         6.5**         13.59   17                                                       7.65**        11.56   173                                                      8.05**        10.99   12                                                       8.35**        10.58   4                                                        9.35*         9.44    72                                                       13.25*        6.67    35                                                       13.7**        6.46    8                                                        14.9**        5.95    8                                                        15.2**        5.82    12                                                       15.65**       5.66    12                                                       16.6**        5.34    13                                                       18.3          4.85    36                                                       19.8**        4.48    4                                                        20.4**        4.35    19                                                       21.1*         4.21    83                                                       21.5**        4.13    36                                                       22.1**        4.018   12                                                       22.75*        3.911   100                                                      23.15**       3.839   19                                                       23.95**       3.716   4                                                        24.2**        3.681   9                                                        24.8**        3.593   3                                                        26.45**       3.369   8                                                        26.8*         3.324   21                                                       27.75**       3.215   6                                                        28.2**        3.162   5                                                        28.7*         3.111   19                                                       29.7*         3.005   15                                                       30.1*         2.970   22                                                       30.6**        2.922   4                                                        31.05**       2.881   7                                                        32.8*         2.731   8                                                        34.3*         2.615   6                                                        34.55**       2.597   10                                                       35.9**        2.502   8                                                        36.45*        2.464   4                                                        38.05*        2.365   5                                                        40.7*         2.217   4                                                        ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) The ZnAPSO-39 compositions are generally characterized by the data of Table XVII-F below.

                  TABLE XVII-F                                                     ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.35-9.45    9.46-9.36 m                                                       13.15-13.35  6.73-6.63 m                                                       18.3-18.4    4.85-4.82 w-m                                                     21.1-21.2    4.21-4.19 s-vs                                                    22.75-22.85  3.909-3.892                                                                              s-vs                                                    26.8-26.9    3.389-3.314                                                                              w-m                                                     ______________________________________                                    

(c) The ZnAPSO-39 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-F below:

    ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.35-9.45     9.46-9.36 60-72                                                  13.15-13.35   6.73-6.63 22-40                                                  18.3-18.4     4.85-4.82 16-40                                                  21.1-21.2     4.21-4.19  83-100                                                22.75-22.85   3.909-3.892                                                                               85-100                                                26.8-26.9     3.389-3.314                                                                              12-40                                                  28.2-28.3     3.164-3.153                                                                              5-8                                                    28.7-28.8     3.110-3.100                                                                              19-20                                                  29.7-29.8     3.008-2.998                                                                              11-32                                                  30.1-30.2     2.979-2.959                                                                              11-25                                                   32.8-32.95   2.730-2.718                                                                               8-12                                                   34.5-34.65   2.600-2.589                                                                              5-6                                                    36.45-36.5    2.465-2.462                                                                               4-12                                                  37.85-38.1    2.377-2.362                                                                               3-10                                                   40.6-40.95   2.222-2.204                                                                              0-4                                                    ______________________________________                                    

EXAMPLE 53F

(a) ZnAPSO-43, as referred to in example 28F, was subjected to x-ray analysis. ZnAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         12.45         7.11    76                                                       14.0*         6.32    194                                                      16.95         5.24    8                                                        19.8*         4.48    160                                                      20.95         4.24    13                                                       21.15*        4.20    13                                                       21.85         4.07    48                                                       22.15*        4.010   8                                                        24.3*         3.659   400                                                      27.1          3.291   100                                                      28.15*        3.171   52                                                       28.75         3.104   4                                                        31.55*        2.837   49                                                       32.55         2.751   20                                                       32.75*        2.733   9                                                        34.25*        2.620   8                                                        34.65*        2.590   68                                                       37.5*         2.399   8                                                        38.5*         2.340   6                                                        40.2*         2.244   16                                                       41.2          2.190   4                                                        42.7*         2.117   16                                                       45.1          2.010   8                                                        47.5*         1.914   18                                                       49.45*        1.843   7                                                        51.15         1.787   7                                                        51.9*         1.761   36                                                       53.8          1.704   7                                                        ______________________________________                                          *Impurity peak                                                           

(b) ZnAPSO-43 compositions are generally characterized by the data of Table XIX-F below:

                  TABLE XIX-F                                                      ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         12.3-12.45   7.20-7.11 m-vs                                                    16.8-16.95   5.28-5.23 vw-w                                                    21.7-21.85   4.095-4.068                                                                              vw-m                                                    26.95-27.1   3.308-3.291                                                                              s-vs                                                    32.4-33.55   2.763-2.751                                                                              w-m                                                     ______________________________________                                    

(c) The ZnAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-F below:

                  TABLE XX-F                                                       ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         12.3-12.45    7.20-7.11  66-100                                                16.8-16.95    5.28-5.23  0-10                                                  20.8-20.95    4.27-4.24 10-13                                                  21.7-21.85    4.095-4.068                                                                               0-48                                                  26.95-27.1    3.308-3.290                                                                               82-100                                                28.65-28.75   3.116-3.105                                                                              11-23                                                  32.4-32.55    2.763-2.751                                                                              18-20                                                  41.2          2.191     0-4                                                    44.95-45.1    2.017-2.010                                                                               8-15                                                  50.95-51.15   1.792-1.786                                                                              0-7                                                    53.7-53.8     1.710-1.707                                                                              0-8                                                    ______________________________________                                    

EXAMPLE 54F

(a) ZnAPSO-44 as prepared in example 34F, was subjected to x-ray analysis. ZnAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         4.95*         17.93   11                                                       8.75*         10.09   sh                                                       9.25*         9.56    sh                                                       9.55          9.25    100                                                      13.05         6.77    13                                                       13.8          6.41    3                                                        16.15         5.49    21                                                       17.4          5.10    3                                                        19.05         4.65    7                                                        19.6*         4.53    2                                                        20.8          4.27    46                                                       21.8          4.08    18                                                       22.65         3.923   4                                                        23.15         3.845   5                                                        24.45         3.638   47                                                       26.25         3.395   14                                                       27.3*         3.266   1                                                        27.9          3.197   7                                                        29.8          2.999   3                                                        30.15         2.962   13                                                       30.9          2.895   31                                                       32.65         2.745   2                                                        33.0          2.716   6                                                        34.9          2.571   2                                                        35.15         2.553   2                                                        35.6          2.523   9                                                        38.7          2.329   2                                                        39.25         2.295   2                                                        40.1          2.247   1                                                        42.25         2.139   3                                                        42.55         2.124   2                                                        43.7          2.072   1                                                        48.2          1.887   3                                                        48.8          1.866   4                                                        50.4          1.811   5                                                        52.0          1.759   1                                                        54.0          1.698   7                                                        ______________________________________                                          *Impurity peak                                                           

(b) A portion of the as-synthesized ZnAPSO-44 of part (a) was calcined in air at 500° C. for about 67 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         9.6           9.23    100                                                      13.0          6.81    34                                                       14.05         6.29    5                                                        16.2          5.48    16                                                       17.95         4.95    30                                                       20.3**        4.37    22                                                       20.8          4.27    52                                                       21.4          4.15    32                                                       22.3          3.987   7                                                        22.75*        3.906   7                                                        23.25         3.826   10                                                       24.75**       3.599   5                                                        25.15         3.538   22                                                       26.15         3.406   11                                                       28.4          3.142   9                                                        28.75**       3.107   7                                                        30.95         2.888   23                                                       31.35*        2.852   15                                                       35.3*         2.542   9                                                        ______________________________________                                          *Peak may contain impurity                                                     **Impurity peak                                                          

(c) The ZnAPSO-44 compositions are generally characterized by the data of Table XXI-F below:

                  TABLE XXI-F                                                      ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                          9.4-9.55    9.41-9.26 vs                                                       12.9-13.05  6.86-6.78 vw-m                                                    20.65-20.8   4.30-4.27 m                                                       21.4-21.8    4.15-4.08 w-m                                                      24.3-25.15  3.663-3.541                                                                              m                                                       30.75-30.95  2.908-2.889                                                                              m                                                       ______________________________________                                    

(d) The ZnAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-F below:

                  TABLE XXII-F                                                     ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                          9.4-9.55     9.41-9.25 100                                                     12.9-13.05   6.86-6.78  8-34                                                   13.6-14.05   6.51-6.30 3-5                                                    16.0-16.2     5.54-5.47 14-21                                                  17.25-17.95   5.14-4.94 0-6                                                    18.95-19.05   4.68-4.66 0-5                                                    20.65-20.8    4.30-4.27 35-52                                                  21.4-21.8     4.15-4.08 18-32                                                  22.55-22.65   3.943-3.926                                                                              4                                                      23.15-23.25   3.842-3.826                                                                               5-10                                                   24.3-25.15   3.663-3.541                                                                              22-47                                                   26.2-26.25   3.414-3.395                                                                               8-14                                                  27.7-28.4     3.220-3.143                                                                              7-9                                                    29.8          2.998-    0-3                                                    30.05-30.15   2.974      0-13                                                  30.75-30.95   2.908-2.889                                                                              23-31                                                  32.65-32.8    2.743-2.730                                                                              0-3                                                    33.0          2.714     0-6                                                    34.9          2.571     0-2                                                    35.15         2.553     0-2                                                    35.3-35.6     2.543-2.522                                                                               9-10                                                  38.7          2.327-2.327                                                                              0-2                                                    39.3-40.2     2.292-2.243                                                                              0-2                                                    40.1          2.249     0-1                                                    42.1-42.3     2.146-2.137                                                                              0-3                                                    42.55         2.127     0-2                                                    43.7          2.071     0-1                                                    48.2          1.888     0-3                                                    48.65-48.8    1.872-1.866                                                                              0-5                                                    50.2-50.4     1.817-1.811                                                                              0-5                                                    52.0          1.759     0-1                                                    53.8- 54.0    1.704-1.698                                                                              0-7                                                    ______________________________________                                    

EXAMPLE 55F

(a) ZnAPSO-46, as referred to in example 8F was subjected to x-ray analysis. ZnAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         6.6           13.39   8                                                        7.75          11.42   100                                                      8.1**         10.90   3                                                        9.45**        9.34    18                                                       10.2          8.67    1                                                        13.35*        6.63    10                                                       13.8          6.41    4                                                        14.95         5.92    4                                                        15.75**       5.62    3                                                        16.7          5.31    7                                                        17.5          5.07    1                                                        18.4**        4.83    10                                                       19.85         4.47    3                                                        20.5*         4.33    6                                                        21.25**       4.19    25                                                       21.6          4.12    18                                                       22.25**       3.998   3                                                        22.8          3.896   32                                                       23.3**        3.818   4                                                        24.05         3.700   3                                                        24.25*        3.669   5                                                        25.3*         3.523   1                                                        26.55**       3.354   3                                                        26.9          3.313   10                                                       27.8          3.207   3                                                        28.3          3.152   2                                                        28.8*         3.100   8                                                        29.85*        2.993   6                                                        30.2**        2.961   7                                                        31.15         2.870   3                                                        31.8*         2.813   1                                                        32.95*        2.719   3                                                        34.3*         2.612   2                                                        34.65**       2.590   3                                                        36.0*         2.495   3                                                        36.55         2.459   2                                                        36.8*         2.442   1                                                        37.3          2.410   1                                                        38.1**        2.361   1                                                        39.7*         2.271   1                                                        40.95*        2.204   1                                                        43.2**        2.093   1                                                        44.1*         2.054   1                                                        46.1*         1.969   1                                                        47.65*        1.908   1                                                        49.45**       1.844   1                                                        49.65*        1.836   1                                                        51.55*        1.772   1                                                        52.45*        1.745   1                                                        ______________________________________                                          *Peak may contain impurity                                                     **Impurity peak                                                          

(b) The ZnAPSO-46 compositions are characterized by the data of Table XXIII-F below:

                  TABLE XXIII-F                                                    ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                          7.6-7.75    11.63-11.42                                                                              vs                                                       13.1-13.35  6.76-6.63 w-m                                                     21.5-21.6    4.13-4.12 w-m                                                      22.6-22.85  3.934-3.896                                                                              m                                                       26.75-27.0   3.333-3.302                                                                              w                                                       ______________________________________                                    

(c) The ZnAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-F below:

                  TABLE XXIV-F                                                     ______________________________________                                         2Θ     d, (Å)                                                                               100 × I/Io                                        ______________________________________                                         6.5-6.7      13.60-13.19                                                                               7-10                                                    7.6-7.75    11.63-11.42                                                                              100                                                     10.2         8.67      0-1                                                      13.1-13.35  6.76-6.63 10-20                                                   13.7-13.8    6.46-6.41 4-5                                                     14.9-15.0    5.95-5.91 4-5                                                      15.2-15.35  5.83-5.77 5-7                                                     16.6-16.8    5.34-5.28  7                                                      17.35-17.5   5.11-5.07 0-1                                                     19.7-20.0    4.51-4.44 2-3                                                     20.3-20.5    4.37-4.33  6-11                                                   21.5-21.6    4.13-4.12 18-21                                                    22.6-22.85  3.934-3.896                                                                              32-58                                                    23.9-24.05  3.723-3.700                                                                              2-3                                                     25.1-25.3    3.548-3.520                                                                              0-1                                                     26.75-27.0   3.333-3.302                                                                              10-12                                                   27.7-28.0    3.220-3.187                                                                              3-4                                                     28.2-28.3    3.175-3.152                                                                              2-3                                                     28.6-28.9    3.121-3.089                                                                               8-11                                                   29.7-29.9    3.008-2.988                                                                              6-9                                                      31.0-31.15  2.885-2.870                                                                              3-4                                                     31.6-31.8    2.831-2.813                                                                              0-1                                                     32.8-33.2    2.730-2.706                                                                              3-4                                                     34.15-34.4   2.626-2.607                                                                              2-4                                                     35.8-36.0    2.508-2.495                                                                              3-4                                                     36.45-36.55  2.464-2.459                                                                              2-3                                                     37.3-37.7    2.410-2.386                                                                              0-2                                                     39.7         2.271     0-1                                                     40.9-41.1    2.206-2.196                                                                              0-1                                                     43.85-44.1   2.065-2.054                                                                              0-1                                                     46.1         1.969     0-1                                                     47.4-47.7    1.918-1.908                                                                              0-1                                                     49.7-49.8    1.834-1.831                                                                              0-1                                                     51.4-51.7    1.778-1.768                                                                              0-1                                                      52.2-52.45  1.752-1.745                                                                              0-1                                                     ______________________________________                                    

EXAMPLE 56F

(a) ZnAPSO-47, as referred to in example 38F, was subjected to x-ray analysis. ZnAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

    ______________________________________                                         2Θ      d,(Å)                                                                              100 × I/Io                                         ______________________________________                                         7.45*         11.88   2                                                        9.45          9.35    93                                                       12.9          6.87    17                                                       13.9          6.38    7                                                        16.0          5.54    42                                                       17.65         5.03    11                                                       19.0*         4.67    3                                                        20.6          4.31    100                                                      21.85         4.07    7                                                        22.4*         3.97    6                                                        23.0          3.867   11                                                       24.75         3.600   21                                                       25.9          3.439   23                                                       27.65         3.228   10                                                       28.0          3.188   3                                                        29.5          3.029   5                                                        30.6          2.922   49                                                       30.9          2.894   sh                                                       31.5          2.839   3                                                        32.3          2.772   2                                                        33.3          2.689   3                                                        34.5          2.600   10                                                       34.9          2.573   2                                                        35.7          2.516   4                                                        38.4          2.344   3                                                        39.65         2.273   4                                                        42.5          2.126   3                                                        43.3          2.089   2                                                        44.9          2.019   2                                                        47.6          1.909   4                                                        48.6          1.873   5                                                        50.5          1.807   5                                                        53.25         1.721   5                                                        54.5          1.684   2                                                        56.0          1.642   5                                                        ______________________________________                                          *Impurity peak                                                           

(b) A portion of the as-synthesized ZnAPSO-47 of part (a) was calcined in air at 500° C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2Θ      d, (Å)                                                                              100 × I/Io                                        ______________________________________                                         7.5*          11.78    11                                                      9.65          9.17     100                                                     13.05         6.78     25                                                      14.15         6.26     3                                                       16.2          5.46     10                                                      18.0          4.93     8                                                       19.25         4.61     3                                                       19.8*         4.49     2                                                       20.85         4.26     27                                                      21.25*        4.18     sh                                                      22.5*         3.950    8                                                       23.3          3.816    4                                                       25.2          3.533    8                                                       26.2          3.399    10                                                      28.0          3.187    2                                                       28.55         3.126    3                                                       29.8          2.998    2                                                       31.0          2.885    18                                                      31.4          2.849    sh                                                      34.9          2.571    2                                                       ______________________________________                                          *Impurity peak                                                           

(c) The ZnAPSO-47 compositions are characterized by the date in Table XXV-F below:

                  TABLE XXV-F                                                      ______________________________________                                         2Θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.45-9.65    9.35-9.17 vs                                                      12.85-13.05  6.89-6.78 w-m                                                     15.95-16.2   5.55-5.46 w-m                                                     20.55-20.85  4.31-4.26 m-vs                                                    25.9-26.2    3.439-3.399                                                                              w-m                                                     30.55-31.0   2.925-2.885                                                                              w-m                                                     ______________________________________                                    

(d) The ZnAPSO-47 compositions for which x-ray powder diffracton data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-F below:

                  TABLE XXVI-F                                                     ______________________________________                                         2Θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.45-9.65     9.35-9.17  93-100                                                12.85-13.05   6.89-6.78 17-25                                                  13.85-14.15   6.39-6.26 3-7                                                    15.95-16.2    5.55-5.46 10-42                                                  17.45-18.0    5.09-4.93 2-11                                                   20.55-20.85   4.31-4.26  27-100                                                 21.85        4.07      0-7                                                    22.95-23.3    3.867-3.816                                                                               4-11                                                  24.75-25.2    3.600-3.533                                                                               8-21                                                  25.9-26.2     3.439-3.399                                                                              16-29                                                   27.6-28.55   3.231-3.126                                                                               3-10                                                  27.9-28.0     3.196-3.188                                                                              0-3                                                    29.45-29.8    3.031-2.998                                                                              2-5                                                    30.55-31.0    2.925-2.885                                                                              18-49                                                  30.9-31.4     2.894-2.849                                                                              sh                                                     31.5          2.839     0-3                                                    32.3          2.772     0-2                                                    33.3          2.689     0-3                                                    34.45-34.9    2.603-2.600                                                                               2-19                                                  34.9          2.573     0-2                                                    35.7-35.9     2.516-2.503                                                                              0-5                                                     38.4-38.55   2.344-2.336                                                                              0-3                                                     39.6-39.65   2.273     0-4                                                    42.25-42.5    2.139-2.126                                                                              0-3                                                    43.3          2.089     0-2                                                    44.9          2.019     0-2                                                    47.6          1.909     0-6                                                    48.6-48.7     1.873-1.870                                                                              0-5                                                    50.45-50.5    1.807     0-5                                                     53.2-53.25   1.722-1.721                                                                              0- 5                                                   54.5          1.684     0-2                                                    56.0          1.642     0-5                                                    ______________________________________                                    

EXAMPLE 57F

In order to demonstrate the catalytic activity of calcined ZnAPSO compositions were tested for catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test ZnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The ZnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of the ZnAPSO compositions. The k_(A) value (cm³ /g min) obtained for the ZnAPSO compositions are set forth, below, in Table XXVII-F:

                  TABLE XXVII-F                                                    ______________________________________                                                      Prepared in                                                       ZnAPSO       Example No.                                                                               Rate Constant (k.sub.A)*                               ______________________________________                                         ZnAPSO-5      4F        1.5                                                    ZnAPSO-34    24F        12.7                                                   ZnAPSO-35    33F        1.0                                                    ZnAPSO-44    35F        5.0                                                    ZnAPSO-47    39F        5.6                                                    ______________________________________                                          *ZnAPSO-5 were calcined prior to in situ activation as follows:                (a) ZnAPSO5: in air at 500° C. for 0.75 and at 600° C. for       1.25 hours;                                                                    (b) ZnAPSO34: in air at 500° C. for 2 hours;                            (c) ZnAPSO35: in air at 500° C. for 1.75 hours;                         (d) ZnAPSO44: in air at 500° C. for 67 hours; and                       (e) ZnAPSO47: in air at 500° C. for 1.75 hours.                   

COBALT-MANGANESE-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES Preparative Reagents

In the following examples the CoMnAPSO compositions were prepared using numerous regents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Aiipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent phosphoric acid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂. 4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

The following preparative examples were carried out by forming a starting reaction mixture by adding the H₃ PO₄ and one half of the quantity of water. To this mixture the aluminum isopropoxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using manganese acetate and one half of the remaining water. A third mixture was prepared using cobalt acetate and one half of the remaining water. The three mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e. about 2 to 4 minutes. The pH of the mixture was measured and adjusted for temperature. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature All digestions were carried out at the autogeneous pressure.

EXAMPLES 1G to 4G

CoMnAPSO molecular sieves were prepared according to the above identified procedure and the CoMnAPSO products determined by X-ray analysis. The results of examples 1G to 4G are set forth in Table I-G. Examples AG to FG in Table I-G represent reaction mixtures that did not show CoMnAPSO products when determined by X-ray analysis.

                                      TABLE I-G                                    __________________________________________________________________________     Example.sup.1                                                                        Template                                                                             Temp (°C.)                                                                    Time (days)                                                                           CoMnMgAPSO Product(s).sup.2                           __________________________________________________________________________     1G    TEAOH 150   2      CoMnAPSO-34; CoMnAPSO-5                               2G    TEAOH 150   7      CoMnAPSO-34; CoMnAPSO-5                               3G    Pr.sub.2 NH                                                                          200   2      CoMnAPSO-5; CoMnAPSO-11                               4G    Pr.sub.2 NH                                                                          200   7      CoMnAPSO-5; CoMnAPSO-11                               AG    TEAOH 100   3        --                                                  BG    TEAOH 100   7        --                                                  CG    Pr.sub.2 NH                                                                          150   2        --                                                  .sup. DG.sup.3                                                                       Pr.sub.2 NH                                                                          150   10       --                                                  .sup. EG.sup.3                                                                       Pr.sub.2 NH                                                                          150   6        --                                                  .sup. FG.sup.3                                                                       Pr.sub.2 NH                                                                          150   15       --                                                  __________________________________________________________________________      .sup.1 The reaction mixture comprised: 1.0 R: 0.2 MnO: 0.2 CoO: 0.8            Al.sub.2 O.sub.3 : 0.8 P.sub.2 O.sub.5 : 0.4 SiO.sub.2 : 50 H.sub.2 O          where "R" is the template.                                                     .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species are identified the first species         listed is present in an amount equal to or greater than the second specie      listed. A "--" indicates that crystalline products were not identified by      Xray analysis.                                                                 .sup.3 X-ray analysis indicated that crystalline product was beginning to      form.                                                                    

EXAMPLE 5G

(a) Samples of the above prepared CoMnAPSO products, as identified in parenthesis, were calcined in air to remove at least part of the organic templating agent of the CoMnAPSO product. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350° C. prior to measurement. The McBain-Bakr data were as follows:

(b) CoMnAPSO-34 and CoMnAPSO-5 (Example 2G):

    ______________________________________                                                  Kinetic    Pressure  Temp  Wt. %                                      Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                         Adsorbed*                                  ______________________________________                                         Oxygen   3.46       105       -183  13.8                                       Oxygen   3.46       733       -183  18.5                                       Neopentane                                                                              6.2        742       23.8  2.6                                        Cyclohexane                                                                             6.0         65       23.7  4.6                                        n-hexane 4.3         93       23.4  5.0                                        H.sub.2 O                                                                               2.65          4.6    23.4  15.8                                       H.sub.2 O                                                                               2.65        19       23.7  23.6                                       ______________________________________                                          *calcined in air at 600° C. for one hour prior to activation      

(c) CoMnAPSO-5 and CoMnAPSO-11

    ______________________________________                                                  Kinetic    Pressure  Temp  Wt. %                                      Adsorbate                                                                               Diameter, Å                                                                           (Torr)    (°C.)                                                                         Adsorbed*                                  ______________________________________                                         Oxygen   3.46       105       -183  5.5                                        Oxygen   3.46       733       -183  9.3                                        Neopentane                                                                              6.2        742       23.8  2.4                                        Cyclohexane                                                                             6.0         65       23.7  5.9                                        H.sub.2 O                                                                               2.65          4.6    23.4  7.4                                        H.sub.2 O                                                                               2.65        19       23.7  16.2                                       ______________________________________                                          *calcined in air at 600° C. for one hour prior to activation      

EXAMPLE 6G

Samples of the as-synthesized products of examples 2G and 4G were subjected to chemical analysis. The chemical analysis for these CoMnAPSOs was:

(a) The chemical analysis for the product of example 2G was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             27.5                                                             P.sub.2 O.sub.5                                                                              37.7                                                             SiO.sub.2     4.98                                                             CoO           4.3                                                              MnO           5.2                                                              Carbon        5.3                                                              LOI*          20.5                                                             ______________________________________                                          *Loss on Ignition                                                        

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:

    0.057CoO:0.073MnO:0.270Al.sub.2 O.sub.3 :0.266P.sub.2 O.sub.5 :0.083SiO.sub.2

and a formula (anhydrous basis) of:

    0.055R(Al.sub.0.420 P.sub.0.414 Si.sub.0.065 Co.sub.0.044 Mn.sub.0.057)O.sub.2.

(b) The chemical analysis for the product of example 4G was:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             26.6                                                             P.sub.2 O.sub.5                                                                              37.6                                                             SiO.sub.2     7.1                                                              CoO           5.1                                                              MnO           6.0                                                              Carbon        1.91                                                             LOI*          17.9                                                             ______________________________________                                          *Loss on Ignition                                                        

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:

    0.068CoO:0.085MnO:0.261Al.sub.2 O.sub.3 :0.265P.sub.2 O.sub.5 :0.118SiO.sub.2

and a formula (anhydrous basis) of:

    0.027R(Al.sub.0.40 P.sub.0.40 Si.sub.0.089 Co.sub.0.051 Mn.sub.0.064)O.sub.2.

EXAMPLE 7G

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on the products of examples 2G and 4G. Analysis of crystals having a morphology characteristic of each CoMnAPSO product gave the following analysis based on relative peak heights:

(a) Example 2G (CoMnAPSO-5):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Al        0.81                                                                 P         0.98                                                                 Si        0.18                                                                 Co        0.10                                                                 Mn        0.17                                                                 ______________________________________                                    

(b) Example 2G (CoMnAPSO-34):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Al        0.82                                                                 P         0.93                                                                 Si        0.17                                                                 Co        0.03                                                                 Mn        0.03                                                                 ______________________________________                                    

(c) Example 4G (CoMnAPSO-5):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Al        0.93                                                                 P         0.71                                                                 Si        0.15                                                                 Co        0.05                                                                 Mn        0.07                                                                 ______________________________________                                    

(d) Example 4G (CoMnAPSO-11):

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Al        0.81                                                                 P         0.95                                                                 Si        0.15                                                                 Co        0.03                                                                 Mn        0.05                                                                 ______________________________________                                    

EXAMPLE 8G

(a) CoMnAPSO-5, as prepared in example 1G, was subjected to x-ray analysis. The CoMnAPSO-5 was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                         7.5           11.84   67                                                       9.5*          9.29    100                                                      12.9**        6.89    11                                                       14.1*         6.29     7                                                       14.9          5.93    14                                                       16.0*         5.54    22                                                       18.0*         4.93    10                                                       19.8          4.49    19                                                       20.6*         4.32    51                                                       21.1**        4.22    40                                                       22.4          3.96    28                                                       25.2*         3.530   12                                                       29.1          3.071    6                                                       29.5*         3.024    3                                                       30.1          2.968   10                                                       30.5*         2.928   16                                                       31.3*         2.862   11                                                       33.7*         2.659    3                                                       34.5          2.601    4                                                       34.6*         2.591    5                                                       37.8          2.383    6                                                       47.7**        1.905    3                                                       48.9*         1.863    2                                                       49.9*         1.828    2                                                       50.9*         1.794    2                                                       55.8          1.647    2                                                       ______________________________________                                          *peak may be an impurity                                                       **impurity peak and CoMnMgAPSO5                                          

(b) A portion of the as-synthesized CoMnAPSO-5 of example 2G was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                         7.5           11.84   32                                                       9.6*          9.20    100                                                      13.0**        6.81    20                                                       14.9          5.93    4                                                        16.2*         5.48    8                                                        18.0*         4.93    6                                                        19.3*         4.60    3                                                        19.8          4.49    8                                                        20.9**        4.26    22                                                       21.2**        4.20    26                                                       21.5*         4.13    3                                                        22.5          3.95    32                                                       23.4*         3.81    3                                                        25.3*         3.520   7                                                        26.1          3.420   11                                                       26.2*         3.396   7                                                        28.5*         3.129   3                                                        29.2          3.063   6                                                        30.2          2.965   6                                                        31.0*         2.881   11                                                       31.5*         2.840   7                                                        34.7          2.584   4                                                        34.9          2.568   3                                                        38.0*         2.368   2                                                        ______________________________________                                          *peak may be an impurity                                                       **impurity peak and CoMnAPSO5                                            

(c) The species CoMnAPSO-5 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II-G as follows:

                  TABLE II-G                                                       ______________________________________                                         2θ     d(Å)  Relative Intensity                                      ______________________________________                                         7.4-7.5      11.95-11.84                                                                              m                                                       12.9-13.1    6.89-6.76 w-m                                                     14.9         5.93      vw-w                                                    19.7-19.8    4.51-4.49 vw-w                                                    20.9-21.3    4.26-4.17 m                                                       22.4-22.5    3.97-3.95 m                                                       ______________________________________                                    

(d) All of the CoMnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have been obtained have patterns which are within the generalized pattern of Table III-G, below:

                  TABLE III-G                                                      ______________________________________                                         2θ     d(Å)  (I/Io) × 100                                      ______________________________________                                         7.4-7.5      11.95-11.84                                                                              32-67                                                   12.9-13.1    6.89-6.81 11-20                                                   14.9         5.93       4-14                                                   19.7-19.8    4.51-4.49  8-19                                                   20.9-21.3    4.26-4.17 22-40                                                   22.4-22.5    3.96-3.95 28-32                                                   24.7-24.8    3.60-3.59 6                                                       25.9-26.1    3.440-3.420                                                                              10-11                                                   29.0-29.2    3.079-3.063                                                                              6                                                       29.9-30.2    2.988-2.965                                                                               6-10                                                   34.4-34.7    2.607-2.584                                                                              4                                                       34.9         2.568     3                                                       37.8         2.383     6                                                       47.7         1.905     3                                                       55.8         1.647     2                                                       ______________________________________                                    

EXAMPLE 9G

(a) The CoMnAPSO-11, prepared in example 3G, was subjected to X-ray analysis. The CoMnAPSO-11 was impure but the CoMnAPSO-11 was determined to have an X-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                         7.0*          12.56   12                                                       7.5*          11.86   68                                                       8.1           10.88   46                                                       9.5           9.31    68                                                       12.9*         6.87    11                                                       13.2          6.73    24                                                       14.9*         5.95    12                                                       15.7          5.64    49                                                       16.3          5.44     9                                                       19.0          4.67     9                                                       19.7*         4.50    29                                                       20.4          4.36    66                                                       21.1**        4.21    37                                                       21.2          4.19    34                                                       22.4*         3.96    41                                                       22.8          3.91    29                                                       23.2          3.83    100                                                      24.8**        3.59    10                                                       25.9*         3.443   23                                                       26.5          3.365   32                                                       28.2          3.163    9                                                       28.7          3.113   25                                                       29.5          3.024    8                                                       29.9*         2.985   15                                                       31.5          2.838    8                                                       32.7          2.739    2                                                       34.2          2.622    2                                                       36.4          2.468    2                                                       37.6          2.392    2                                                       ______________________________________                                          *peak may be an impurity                                                       **impurity peak                                                          

(b) A portion of the as-synthesized CoMnAPSO-11 of example 4G was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the following X-ray powder diffraction pattern:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                         7.5*          11.86    95                                                      8.2           10.85    68                                                      9.6           9.19     95                                                      13.1*         6.77     45                                                      15.9          5.58     91                                                      19.8*         4.48     32                                                      20.3          4.37     49                                                      21.3*         4.17     34                                                      22.5**        3.96     62                                                      23.4          3.80     100                                                     26.0*         3.423    43                                                      26.4          3.376    40                                                      26.6          3.346    16                                                      29.1*         3.073    27                                                      29.2          3.061    28                                                      30.2*         2.962    21                                                      32.8          2.732    21                                                      32.9          2.719    31                                                      34.7*         2.586    28                                                      36.2          2.481     2                                                      ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The species CoMnAPSO-11 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IV-G as follows:

                  TABLE IV-G                                                       ______________________________________                                         2θ     d, (Å)                                                                              Relative Intensity                                       ______________________________________                                         9.5-9.6      9.31-9.21                                                                               m-vs                                                     15.7-15.9    5.64-5.57                                                                               m-vs                                                     20.3-20.4    4.37-4.36                                                                               m                                                        21.1-21.2    4.21-4.19                                                                               m                                                        22.1-22.5    4.02-3.95                                                                               m                                                        23.2-23.4    3.83-3.80                                                                               vs                                                       ______________________________________                                    

(d) All of the CoMnAPSO-11 compositions both as-synthesized and calcined, for which x-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table V-G, below:

                  TABLE V-G                                                        ______________________________________                                         2θ     d, (Å)                                                                               (I/Io) × 100                                      ______________________________________                                         8.1-8.2      10.88-10.85                                                                              46-48                                                   9.5-9.6      9.31-9.19 68-95                                                   13.1-13.2    6.77-6.73 24-45                                                   15.7-15.9    5.64-5.58 49-91                                                   16.3         5.44      9                                                       19.0         4.67       9-10                                                   20.3-20.4    4.37-4.36 49-66                                                   21.1-21.2    4.21-4.19 30-37                                                   22.1-22.5    4.02-3.96 31-62                                                   22.7-22.8    3.92-3.91 28-29                                                   23.2-23.4    3.83-3.80 100                                                     24.7-24.8    3.60-3.59 10-14                                                   26.4-26.6    3.376-3.346                                                                              16-40                                                   28.1-28.2    3.175-3.163                                                                              9                                                       28.7         3.113     25-26                                                   29.2-29.5    3.061-3.024                                                                               8-28                                                   31.5         2.838     8                                                       32.7-32.8    2.739-2.732                                                                               2-27                                                   32.9         2.719     31                                                      34.2         2.622      2-11                                                   36.2-36.4    2.481-2.468                                                                              2-9                                                     37.6-37.9    2.392-2.374                                                                              2-3                                                     ______________________________________                                    

EXAMPLE 10G

(a) The CoMnAPSO-34, prepared in example 1G, was subjected to x-ray analysis. The CoMnAPSO-34 was impure but was the major phase and was determined to have an x-ray powder diffraction pattern characterized by the following data:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                         7.5*          11.84   67                                                       9.5           9.29    100                                                      12.9**        6.89    11                                                       14.1          6.29     7                                                       14.9*         5.93    14                                                       16.0          5.54    22                                                       18.0          4.93    10                                                       19.8*         4.49    19                                                       20.6          4.32    51                                                       21.1**        4.22    40                                                       22.4*         3.96    28                                                       25.2          3.530   12                                                       29.1*         3.071    6                                                       29.5          3.024    3                                                       30.1*         2.968   10                                                       30.5          2.928   16                                                       31.3          2.862   11                                                       33.7          2.659    3                                                       34.5*         2.601    4                                                       34.6          2.591    5                                                       37.8*         2.383    6                                                       47.7**        1.905    3                                                       48.9          1.863    2                                                       49.9          1.828    2                                                       50.9          1.794    2                                                       55.8*         1.647    2                                                       ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(b) A portion of the as-synthesized CoMnAPSO-34 of 2G was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

    ______________________________________                                         2θ      d(Å)                                                                               (I/Io) × 100                                       ______________________________________                                          7.5*         11.84   32                                                        9.6          9.20    100                                                       13.0**       6.81    20                                                        14.9*        5.93    4                                                        16.2          5.48    8                                                        18.0          4.93    6                                                        19.3          4.60    3                                                         19.8*        4.49    8                                                         20.9**       4.26    22                                                        21.2**       4.20    26                                                       21.5          4.13    3                                                         22.5*        3.96    32                                                       23.4          3.81    3                                                        25.3          3.520   7                                                         26.1*        3.420   11                                                       26.2          3.396   7                                                        28.5          3.129   3                                                         29.2*        3.063   6                                                         30.2*        2.965   6                                                        31.0          2.881   11                                                       31.5          2.840   7                                                         34.7*        2.584   4                                                         34.9*        2.568   3                                                        38.0          2.368   2                                                        ______________________________________                                          *peak may contain impurity                                                     **impurity peak                                                          

(c) The species CoMnAPSO-34 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VI-G as follows:

                  TABLE VI-G                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.5-9.6      9.29-9.20 vs                                                      12.8-13.0    6.92-6.81  w-m                                                    16.0-16.2    5.54-5.48 vw-m                                                    20.6-20.9    4.32-4.26 m                                                       21.1-21.2    4.22-4.20 m                                                       25.2-25.3    3.530-3.520                                                                              vw-w                                                    31.0-31.5    2.881-2.840                                                                              w                                                       ______________________________________                                    

(d) All of the CoMnAPSO-34 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have been obtainehave patterns which are within the generalized pattern below:

                  TABLE VII-G                                                      ______________________________________                                         2θ     d(Å)  (I/Io) × 100                                      ______________________________________                                         9.5-9.6      9.29-9.20 100                                                     12.8-13.0    6.92-6.81 11-20                                                   14.1         6.29      7-9                                                     16.0-16.2    5.54-5.48  8-23                                                   18.0         4.93       6-12                                                   19.3         4.60      3                                                       20.6-20.9    4.32-4.26 22-57                                                   21.1-21.2    4.22-4.20 26-40                                                   21.5         4.13      3                                                       23.0-23.4    3.87-3.81 2-3                                                     25.2-25.3    3.530-3.520                                                                               7-14                                                   25.8-26.2    3.453-3.396                                                                               7-13                                                   27.5         3.243     2                                                       28.3-28.5    3.153-3.129                                                                              3-4                                                     29.5         3.024     3                                                       30.5         2.928     16-18                                                   31.0-31.5    2.881-2.840                                                                              11-13                                                   33.7-33.8    2.659-2.652                                                                              2-7                                                     34.5-34.6    2.601-2.592                                                                              5                                                       38.0         2.368     2                                                       39.6         2.276     2                                                       43.3         2.090     2                                                       47.5-47.7    1.914-1.905                                                                              2-3                                                     48.9-49.0    1.863-1.859                                                                              2-4                                                     49.9         1.828     2                                                       50.8-50.9    1.797-1.794                                                                              2-3                                                     ______________________________________                                    

EXAMPLE 15G

In order to demonstrate the catalytic activity of the CoMnAPSO compositions, calcined samples of the products of examples 2G and 4G, were tested for catalytic cracking. The CoMnAPSO compositions were evaluated for n-butane cracking using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the CoMnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k_(A)) was calculated to determine the relative catalytic activity of each CoMnAPSO composition. The k_(A) value (cm³ /g min) obtained for the CoMnAPSO are set forth below:

    ______________________________________                                         Product of Example No.                                                                          Rate Constant (k.sub.A)**                                     ______________________________________                                         2G*              6.9                                                           4G*              0.8                                                           ______________________________________                                          *calcined at 600° C. in air for 1.5 hours prior to activation.          **(cm.sup.3 /gram minute)                                                

COBALT-MANGANESE-MAGNESIUM-ALUMINUM-PHOSPHORUS-SILICONE-OXIDE SIEVES

Molecular sieves containing coblat, manganese, magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents

In the following examples the CoMnMgAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of Du Pont for an aqueous solution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : aqueous solution which is 85 weight percent phosphoric acid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(f) MgAc: Magnesium Acetate Mg(C₂ H₃ O₂).4H₂ O;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

The following preparative examples were carried out by forming a starting reaction mixture by adding the H₃ PO₄ and one half of the quantity of water. To this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.

Three additional mixtures were prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture. The four mixtures were then admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components with H₃ PO₄ be given as P₂ O₅.

EXAMPLES 1H to 4H

CoMnMgAPSO molecular sieves were prepared according to the above identified procedure and the CoMnMgAPSO products determined by X-ray analysis. The results of preparative examples 1H to 4H are set forth in Table I-H. Examples AH, BH and CH of Table I-H did not contain a product identifiable by x-ray analysis.

                                      TABLE I-H                                    __________________________________________________________________________     Example.sup.1                                                                       Template                                                                            Temp(°C.)                                                                     Time(days)                                                                           CoMnMgAPSO Product(s).sup.2                              __________________________________________________________________________     1H   TEAOH                                                                               100   7     CoMnMgAPSO-34                                            2H   TEAOH                                                                               150   2     CoMnMgAPSO-34; CoMnMgAPSO-5                              3H   TEAOH                                                                               150   7     CoMnMgAPSO-34; CoMnMgAPSO-5                              4H   Pr.sub.2 NH                                                                         200   13    CoMnMgAPSO-11                                            AH   TEAOH                                                                               100   2       --                                                     BH   Pr.sub.2 NH                                                                         150   3       --                                                     CH   Pr.sub.2 NH                                                                         150   10      --                                                     __________________________________________________________________________      .sup.1 Reaction mixture comprised: 1.0 R:0.2 MnO:0.2 CoO:0.2 MgO:0.7           Al.sub.2 O.sub.3 :0.8 P.sub.2 O.sub.5 :0.4 SiO.sub.2 :50H.sub.2 O where        "R" is the template.                                                           .sup.2 Major species as identified by xray powder diffraction pattern of       product, except that when two species are identified the species are           listed in the order of their predominance in the product. A "--" indicate      no CoMnMgAPSO product was indentified by xray analysis.                  

EXAMPLE 5H

Portions of the products of examples 3H and 4H were calcined in air at 600° C. for 1.5 hour to remove at least part of the organic templating agent. The adsorption capacities of each calcined sample were measured using a standard McBain-Baker gravimetric adsorption apparatus. The samples were activated in a vacuum (less than about 0.04 torr) at 350° C. prior to measurement. The McBain-Baker data for the CoMnMgAPSO products were:

(a) Example 3H (CoMnMgAPSO-34 and CoMnMgAPSO-5):

    ______________________________________                                                  Kinetic    Pressure Temp.    Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                            Adsorbed                                 ______________________________________                                         Oxygen   3.46       105      -183     6.0                                      Oxygen   3.46       733      -183     8.4                                      Neopentane                                                                              6.2        742      23.8     1.4                                      Cyclohexane                                                                             6.0        65       23.7     2.6                                      n-hexane 6.0        93       23.4     3.3                                      H.sub.2 O                                                                               2.65       4.6      23.4     7.3                                      H.sub.2 O                                                                               2.65       19       23.7     12.0                                     ______________________________________                                    

(b) Example 4H: (CoMnMgAPSO-11)

    ______________________________________                                                  Kinetic    Pressure Temp     Wt. %                                    Adsorbate                                                                               Diameter, Å                                                                           (Torr)   (°C.)                                                                            Adsorbed                                 ______________________________________                                         Oxygen   3.46       105      -183     2.9                                      Oxygen   3.46       733      -183     3.6                                      Neopentane                                                                              6.2        742      23.8     0.5                                      Cyclohexane                                                                             6.0        65       23.7     2.1                                      H.sub.2 O                                                                               2.65       4.6      23.4     4.1                                      H.sub.2 O                                                                               2.65       19       23.7     9.1                                      ______________________________________                                    

EXAMPLE 6H

Portions of the products of examples 3H and 4H were subjected to chemical analysis. The chemical analyses were as follows:

(a) Example 3H:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             21.5                                                             P.sub.2 O.sub.5                                                                              40.3                                                             SiO.sub.2     6.5                                                              CoO.sup.2     4.58                                                             MnO           4.41                                                             MgO           2.43                                                             Carbon        6.9                                                              LOI*          18.3                                                             ______________________________________                                          *Loss on Ignition                                                        

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:

    0.575R:0.061CoO:0.062MnO:0.060MgO:0.211Al.sub.2 O.sub.3 :0.284P.sub.2 O.sub.5 :0.108SiO.sub.2

and a formula (anhydrous basis) of:

    0.072R(Co.sub.0.048 Mn.sub.0.048 Mg.sub.0.047 Al.sub.0.33 P.sub.0.44 Si.sub.0.084)O.sub.2.

(b) Example 4H:

    ______________________________________                                         Component     Weight Percent                                                   ______________________________________                                         Al.sub.2 O.sub.3                                                                             24.3                                                             P.sub.2 O.sub.5                                                                              41.8                                                             SiO.sub.2     8.5                                                              CoO           6.0                                                              MnO           6.8                                                              MgO           2.8                                                              Carbon        1.54                                                             LOI*          9.3                                                              ______________________________________                                          *Loss on Ignition                                                        

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:

    0.128R:0.08CoO:0.096MnO:0.070MgO:0.238Al.sub.2 O.sub.3 :0.294P.sub.2 O.sub.5 :0.141S:O.sub.2

and a formula (anhydrous basis) of:

    0.0213R(Co.sub.0.055 Mn.sub.0.066 Mg.sub.0.048 Al.sub.0.33 P.sub.0.41 Si.sub.0.097)O.sub.2.

EXAMPLE 7H

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of products from examples 3H and 4H. Analysis of crystals having a morphology characteristic of CoMnMgAPSO-5, CoMnMgAPSO-11, and CoMnMgAPSO-34 gave the following analysis based on relative peak heights:

(a) CoMnMgAPSO-5:

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Co        0.11                                                                 Mn        0.16                                                                 Mg        0.08                                                                 Al        0.55                                                                 P         1.0                                                                  Si        0.11                                                                 ______________________________________                                    

(b) CoMnMgAPSO-11:

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Co        0.09                                                                 Mn        0.06                                                                 Mg        0.11                                                                 Al        0.85                                                                 P         0.99                                                                 Si        0.38                                                                 ______________________________________                                    

(c) CoMnMgAPSO-34:

    ______________________________________                                                 Average of Spot Probes                                                 ______________________________________                                         Co        0.05                                                                 Mn        0.03                                                                 Mg        0.05                                                                 Al        0.81                                                                 P         1.0                                                                  Si        0.20                                                                 ______________________________________                                    

EXAMPLE 8H

(a) CoMnMgAPSO-5, as prepared to in example 3H, was subjected to x-ray analysis and was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ      d(Å)                                                                               100 × I/Io                                         ______________________________________                                         7.4           11.89   15                                                        9.5*         9.27    100                                                       12.8**       6.90    19                                                       14.1*         6.28    14                                                       14.9          5.96    6                                                        16.0*         5.54    46                                                       18.1*         4.90    28                                                       19.2*         4.63    12                                                       19.7          4.50    16                                                       20.6*         4.32    92                                                       21.1          4.20    13                                                       22.4*         3.97    22                                                       22.6          3.94    5                                                        23.1*         3.85    6                                                        25.2*         3.529   28                                                        25.8**       3.454   32                                                       27.6*         3.237   4                                                        28.4*         3.142   4                                                        29.0          3.079   5                                                        29.5*         3.025   4                                                        29.9          2.987   7                                                         30.5**       2.930   37                                                       31.3*         2.863   25                                                       32.4*         2.767   26                                                        34.4**       2.608   11                                                       35.4*         2.537   5                                                        36.3*         2.473   5                                                        37.8          2.382   4                                                        38.7*         2.329   6                                                        38.8*         2.323   6                                                        39.6*         2.276   5                                                        43.3*         2.088   5                                                        45.1          2.010   3                                                        46.1*         1.971   4                                                        46.3          1.962   5                                                        47.2*         1.924   7                                                        48.7          1.870   6                                                        48.9*         1.863   6                                                        51.0*         1.791   4                                                        53.0*         1.728   4                                                        53.1*         1.726   4                                                        ______________________________________                                          *peak may be an impurity                                                       **impurity peak and CoMnMgAPSO5                                          

(b) A portion of the as-sythesized CoMnMgAPSO-5 of part (a) was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.5           11.76   100                                                       9.7*         9.14    86                                                        13.1**       6.79    18                                                       15.0          5.90    30                                                       16.3*         5.44     8                                                       18.1*         4.90     7                                                       19.9          4.47    19                                                        21.2**       4.19    35                                                       21.5*         4.13    44                                                       22.6          3.94    37                                                       23.0*         3.87     6                                                       26.1           3.414  21                                                       26.4*          3.379   9                                                       29.2           3.060   8                                                       30.2           2.956  59                                                       31.2*          2.871  12                                                       31.7*          2.819   7                                                       34.7           2.582  13                                                       35.5*          2.528  16                                                       ______________________________________                                          *peak may be an impurity                                                       **impurity peak and CoMnMgAPSO5                                          

(c) The species CoMnMgAPSO-5 is a molecular sieve having a three-dimensional microporous framework structure of CoO₂ ⁻², MnO₋₂ ⁻², MgO₂ ⁻², AlO₂ ⁻, PO₂ ⁺, and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II-H:

                  TABLE II-H                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         7.4-7.5      11.89-11.76                                                                              .sup. w-vs                                              14.9-15.0    5.96-5.90 vw-m                                                    19.7-19.9    4.50-4.47 w                                                       21.1-21.2    4.20-4.19  w-m                                                    22.6         3.94      vw-m                                                    29.9-30.2    2.987-2.956                                                                              vw-m                                                    ______________________________________                                    

(d) The CoMnMgAPSO-5 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the data of Table III-H below:

                  TABLE III-H                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         7.4-7.5       11.89-11.76                                                                                15-100.0                                             12.8-13.1     6.90-6.79 16-19                                                  14.9-15.0     5.96-5.90  6-30                                                  19.7-19.9     4.50-4.47 16-19                                                  21.1-21.2     4.20-4.19 10-35                                                  22.6          3.94       5-37                                                  25.8-26.1     3.454-3.414                                                                              18-32                                                  29.0-29.2     3.079-3.060                                                                              4-8                                                    29.9-30.2     2.987-2.956                                                                               7-59                                                  30.5          2.930     28-37                                                  34.4-34.7     2.608-2.582                                                                              11-14                                                  37.8          2.382     4                                                      45.1          2.010     3                                                      46.3          1.962     5                                                      48.7          1.870     6                                                      ______________________________________                                    

EXAMPLE 9H

(a) CoMnMgAPSO-11, as prepared in example 4H was subjected to x-ray analysis. CoMnMgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.1           10.95   21                                                       9.5           9.35    34                                                       13.1          6.75    9                                                        15.7          5.66    22                                                       20.3          4.37    29                                                       21.1          4.21    75                                                       22.1          4.02    34                                                       22.4          3.97    27                                                       22.7          3.92    34                                                       23.1          3.84    53                                                       24.7          3.61    7                                                        26.4          3.374   23                                                       27.6*         3.234   100                                                      28.6          3.124   75                                                       32.7          2.736   13                                                       35.2          2.548   20                                                       37.5          2.396   8                                                        37.8          2.383   9                                                        37.9          2.373   7                                                        40.1          2.247   12                                                       45.0          2.013   11                                                       45.2          2.006   18                                                       45.3          2.001   20                                                       45.8          1.983   13                                                       45.9          1.977   13                                                       50.4          1.812   10                                                       50.6          1.803   15                                                       ______________________________________                                          *peak may contain an impurity                                            

(b) A portion of the as-sythesized of part (a) was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern of below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         8.1           10.95   31                                                       9.6           9.23    43                                                       13.0          6.80    30                                                       15.8          5.60    37                                                       20.2          4.40    27                                                       21.3          4.18    100                                                      22.3          3.99    65                                                       23.0          3.87    36                                                       23.4          3.80    50                                                       24.4          3.65    11                                                       26.3          3.392   25                                                       28.3          3.157   83                                                       28.9          3.090   17                                                       29.1          3.067   11                                                       32.8          2.734   19                                                       34.3          2.614   12                                                       37.9          2.373   12                                                       39.0          2.309   15                                                       39.3          2.294   14                                                       44.8          2.025   16                                                       44.9          2.021   17                                                       ______________________________________                                    

(c) The species CoMnMgAPSO-11 is a molecular sieve having three-dimensional microporous framework structures of CoO₂ ⁻², MnO₂ ⁻², MgO₂ ⁻², AlO₂ ⁻, PO₂ ⁺, and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ wherein "R" represents an organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of "R" present per mole of (Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder pattern which contains at least the d-spacings set forth in Table IV-H:

                  TABLE IV-H                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.5-9.6      9.35-9.23 m                                                       15.7-15.8    5.66-5.60 m                                                       21.1-21.4    4.21-4.15 m-vs                                                    22.1-22.3    4.02-3.99 m                                                       22.7         3.92      m-vs                                                    23.3-23.4    3.82-3.80 m                                                       28.3-28.7    3.157-3.110                                                                              m-s                                                     ______________________________________                                    

(d) The CoMnMgAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table V-H below:

                  TABLE V-H                                                        ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         8.1-8.2       10.95-10.65                                                                              17-31                                                  9.5-9.6       9.35-9.23 34-46                                                  13.0-13.3     6.80-6.66  9-30                                                  15.7-15.8     5.66-5.60 22-37                                                  20.2-20.4     4.40-4.35 27-29                                                  21.1-21.4     4.21-4.15  75-100                                                22.1-22.3     4.02-3.99 34-65                                                  22.4          3.97      27                                                     22.7          3.92       34-100                                                23.0-23.2     3.87-3.83 36-53                                                  23.3-23.4     3.82-3.80 50-70                                                  24.4-24.7     3.65-3.61  7-11                                                  26.3-26.5     3.392-3.363                                                                              23-25                                                  28.3-28.7     3.157-3.110                                                                              75-83                                                  28.9          3.090     16                                                     29.1-30.4     3.067-2.940                                                                              11-14                                                  32.7-32.8     2.739-2.734                                                                              13-19                                                  34.3          2.614     12                                                     35.2          2.548     20                                                     37.5-37.8     2.398-2.383                                                                              8                                                      37.9          2.373      7-12                                                  39.0          2.309     15                                                     39.3-40.1     2.294-2.247                                                                              12-16                                                  44.8-45.0     2.025-2.013                                                                              11-17                                                  45.2          2.006     18                                                     45.3          2.001     20                                                     45.8          1.983     13                                                     45.9          1.977     13                                                     50.4          1.812     10                                                     50.6          1.803     15                                                     ______________________________________                                    

EXAMPLE 10H

(a) CoMnMgAPSO-34, as prepared in example 3H, was subjected to x-ray analysis. CoMnMgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains ao least the d-spacings set forth below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.4*          11.89   15                                                       9.5           9.31    100                                                      12.8**        6.90    19                                                       14.1          6.28    14                                                       14.9*         5.96    6                                                        16.0          5.54    46                                                       18.1          4.90    28                                                       19.2          4.62    12                                                       19.7*         4.50    16                                                       20.6          4.32    92                                                       21.1*         4.20    13                                                       22.4          3.97    22                                                       22.6*         3.94    5                                                        23.1          3.85    6                                                        25.2          3.534   28                                                       25.8**        3.454   32                                                       27.6          3.237   4                                                        28.4          3.142   4                                                        29.0*         3.079   5                                                        29.5          3.025   4                                                        29.9*         2.987   7                                                        30.5**        2.930   37                                                       31.3          2.863   25                                                       32.4          2.767   26                                                       34.4**        2.608   11                                                       35.4*         2.537   5                                                        36.3          2.473   5                                                        37.8*         2.382   4                                                        38.7*         2.329   6                                                        38.8          2.323   6                                                        39.6          2.276   5                                                        43.3          2.088   5                                                        45.1*         2.010   3                                                        46.1*         1.971   4                                                        46.3*         1.962   5                                                        47.2          1.924   7                                                        48.7*         1.870   6                                                        48.9          1.863   6                                                        51.0          1.791   4                                                        53.0          1.728   4                                                        53.1          1.726   4                                                        ______________________________________                                          *peak may contain impurity                                                     **peak contains impurity and CoMnMgAPSO34                                

(b) A portion of the as-synthesized CoMnMgAPSO-34 of part (a) was calcined in air at 600° C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern below:

    ______________________________________                                         2θ      d, (Å)                                                                             100 × I/Io                                         ______________________________________                                         7.5*          11.76   100                                                      9.7           9.14    86                                                       13.1**        6.79    18                                                       15.0*         5.90    30                                                       16.3          5.44    8                                                        18.1          4.90    7                                                        19.9*         4.47    19                                                       21.2**        4.19    35                                                       21.5          4.13    44                                                       22.6*         3.94    37                                                       23.0          3.87    6                                                        26.1**        3.414   21                                                       26.4          3.379   9                                                        29.2*         3.060   8                                                        30.2*         2.956   59                                                       31.2          2.871   12                                                       31.7          2.819   7                                                        34.7*         2.582   13                                                       35.5          2.528   16                                                       ______________________________________                                          *peak may contain impurity                                                     **peak contains impurity and CoMnMgAPSO34                                

(c) The species CoMnMgAPSO-34 is a molecular sieve having a three-dimensional microporous framework structure of CoO₂ ⁻², MnO₂ ⁻², MgO₂ ⁻², AlO₂ ⁻, PO₂ ⁺, and SiO₂ tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VI-H:

                  TABLE VI-H                                                       ______________________________________                                         2θ     d, (Å)                                                                               Relative Intensity                                      ______________________________________                                         9.5-9.7      9.31-9.14 vs                                                      16.0-16.3    5.54-5.44 m                                                       20.5-21.2    4.33-4.19 m-s                                                     21.5         4.13      m                                                       25.2         3.534     m                                                       30.2-30.5    2.960-2.930                                                                              m                                                       ______________________________________                                    

(d) The CoMnMgAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table VII-H below:

                  TABLE VII-H                                                      ______________________________________                                         2θ      d, (Å)                                                                               100 × I/Io                                       ______________________________________                                         9.5-9.7       9.31-9.14 100                                                    12.8-13.1     6.90-6.79 13-19                                                  14.1          6.28      12-14                                                  16.0-16.3     5.54-5.44 31-46                                                  18.0-18.1     4.93-4.90 21-28                                                  19.2          4.62       5-12                                                  20.5-21.2     4.33-4.19 61-92                                                  21.5          4.13      44                                                     22.4          3.97       4-25                                                  23.0-23.1     3.87-3.85 4-6                                                    25.2          3.534     21-28                                                  25.8-26.1     3.453-3.414                                                                              13-32                                                  26.4          3.379     9                                                      27.6          3.237     4                                                      28.4          3.142     4-5                                                    29.5          3.025     4                                                      30.2-30.5     2.960-2.930                                                                              21-37                                                  31.2-31.3     2.871-2.863                                                                              14-25                                                  31.7          2.819     7                                                      32.4          2.767     15-26                                                  34.4          2.608      5-11                                                  35.5          2.528     16                                                     36.3          2.473     4-5                                                    38.8          2.323     6                                                      39.6          2.276     5                                                      43.3          2.088     5                                                      47.2-47.5     1.924-1.916                                                                              4-7                                                    48.9          1.863     4-6                                                    51.0          1.791     4                                                      53.0          1.728     4                                                      53.1          1.726     4                                                      ______________________________________                                    

EXAMPLE 11H

The catalytic activity of the CoMnMgAPSO compositions of examples 3H and 4H were evaluated in n-butane cracking using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length an 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoMnMgAPSO's which were 20-40 mesh (U.S. Std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnMgAPSO samples were calcined in air at 600° C. for 1.5 hours to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. From the analytical data the pseudo-first-order rate constants (k.sub. A) were calculated and are set forth in Table VIII-H below:

                  TABLE VIII-H                                                     ______________________________________                                         Product of Ex. No.:                                                                           Rate Constant (k.sub.A)**                                       ______________________________________                                         3H*            8.8                                                             4H*            0.2                                                             ______________________________________                                          *calcined at 600° C. in air for 1.5 hours                               **(cm.sup.3 /gram minute)                                                

PROCESS APPLICATIONS

The ELAPSO compositions of the instant invention exhibit novel surface selectivity characteristics which render them useful as catalysts or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4 Å are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by ELAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.

Using ELAPSO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400° F. to 825° F. using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.

The ELAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700° F. to 1000° F., hydrogen pressures of from 100 to 500 p.s.i.g., LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerizations processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200° F. to 600° F., preferably 300° F. to 550° F. with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F., preferably 850° F. to 950° F. and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C₇ -C₂₀. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesireable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structures of the present ELAPSO catalysts and their availability in a form having very low alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400° to 750° F., pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with ELAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850° to 1100° F., LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the ELAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800°-1000° F. are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like any of which may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500°-900° F., while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700°-1000° F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the ELAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the ELAPSO compositions having pores of at least 5 Å are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350° F. and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700° F. The temperature is preferably at least 450° F. and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250° F. but is preferably at least 350° F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

As stated the ELAPSO molecular sieves of this invention are useful as adsorbents, i.e., separate mixtures of molecular species. Prior to use in such a separation process, the crystalline materials are activated to remove at least some of any molecular species, e.g., templating agent, which may be present in the intracrystalline pore system as a result of synthesis. This may be accomplished by calcining as generally described above, and more specifically in Examples 109A, 109B, 44C, etc.

The ELAPSO molecular sieves of this invention are capable of separating mixtures of molecular species based on the molecular size (kinetic diameters) or on the degree of polarity of the molecular species. When the separation of molecular species is based on molecular size the crystalline microporous material is chosen in view of the dimensions of its pores such that at least the smallest molecular specie of the mixture can enter the intracrystalline void space while at least the largest specie is excluded.

When the separation is based on degree of polarity, it is generally the case that the hydrophillic ELAPSO molecular sieves of this invention will preferentially adsorb the more polar molecular species of a mixture having different degrees of polarity even though both molecular species can communicate with the pore system of the crystalline material. For example water, which is more polar, will be preferentially adsorbed over common hydrocarbon molecules. 

We claim:
 1. A process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture of molecular species with a molecular sieve having pore diameters large enough to adsorb at least one of the more polar molecular species, said molecular sieve being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof, said molecular sieve being a crystalline molecular sieve having a three-dimensional microporous framework structure of ELO₂, AlO₂, PO₂, SiO₂ oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having an "M-O" bond dissociation energy greater than about 59 kcal/mole at 298° C.; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus, and silicon, respectively, present as framework oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, wherein element "EL" and each of aluminum, phosphorus and silicon are present such that "w", "x", "y" and "z" are at least 0.01 and each element "EL" is present as a tetrahedral oxide unit ELO₂ in an amount of at least 0.01.
 2. Process according to claim 1 wherein the more polar molecular species is water.
 3. A process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a molecular sieve having pore diameters large enough to adsorb at least one but not all molecular species of said mixture, said molecular sieve being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof, said molecular sieve being a crystalline molecular sieve having a three-dimensional microporous framework structure of ELO₂, AlO₂, PO₂, SiO₂ oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value of zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having an "M-O" bond dissociation energy greater than about 59 kcal/mole at 298° C.; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus, and silicon, respectively, present as framework oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, wherein element "EL" and each of aluminum, phosphorus and silicon are present such that "w", "x", "y" and "z" are at least 0.01 and each element "EL" is present as a tetrahedral oxide unit ELO₂ in an amount of at least 0.01. 